Treatment Liquid Composition, Set, Ink Jet Printing Method, And Cloth

ABSTRACT

A treatment liquid composition is a treatment liquid composition which is used to be adhered to a cloth and which includes a cationic compound, a water-soluble resin, and water; a molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum peak in a molecular weight range of 28,000 to 2,800,000; and a content of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to a total mass of the treatment liquid composition.

The present application is based on, and claims priority from, JPApplication Serial Number 2018-143267, filed Jul. 31, 2018, thedisclosure of which is hereby incorporated by reference herein in itsentirety.

BACKGROUND 1. Technical Field

The present disclosure relates to a treatment liquid composition, a set,an ink jet printing method, and a cloth.

2. Related Art

Heretofore, when a printed material is formed by dyeing a substrate,such as a cloth, with a colorant, in order to improve a chromogenicproperty of the colorant, a technique in which a pre-treatment isperformed on the substrate using a treatment liquid which contains acationic compound and the like has been known. For example,JP-A-2008-266853 has proposed as the treatment liquid described above,an ink jet-printing pre-treatment agent which contains a water-solublepolyvalent metal salt and a specific resin emulsion.

However, in recent years, a printed material formed by ink jet printinghas been required to have a higher chromogenic property, and accordingto the treatment liquid disclosed in JP-A-2008-266853, a problem in thata sufficient improvement in chromogenic property is not obtained in somecases may arise. In addition, in order to improve the chromogenicproperty of the colorant of the printed material, when the contents ofthe water-soluble polyvalent metal salt and the specific resin emulsionin the treatment liquid are increased, the viscosity of the treatmentliquid composition is disadvantageously liable to be increased.

SUMMARY

According to several aspects of the present disclosure, since theproblems described above are overcome, a treatment liquid compositionhaving a preferable viscosity, a set, an ink jet printing method, and acloth, each of which can obtain a printed material having an excellentchromogenic property, are provided.

A treatment liquid composition of the present disclosure is a treatmentliquid composition which is used to be adhered to a cloth and whichcomprises a cationic compound, a water-soluble resin, and water; amolecular weight distribution of a water-soluble component contained inthe treatment liquid composition has a maximum peak in a molecularweight range of 28,000 to 2,800,000; and a content of a water-solubleresin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0percent by mass with respect to a total mass of the treatment liquidcomposition.

According to the treatment liquid composition described above, themolecular weight distribution of the water-soluble component may furtherhave a maximum peak in a molecular weight range of 1,000 to 25,000, andthe ratio of a peak area of a molecular weight of 28,000 to 2,800,000 toa peak area of a molecular weight of 1,000 to 25,000 may be 1:5 to 5:1.

According to the treatment liquid composition described above, thewater-soluble resin may be at least one selected from a poly(ethyleneoxide), a carboxymethyl cellulose, a hydroxyethyl cellulose, and apoly(vinyl pyrrolidone).

The treatment liquid composition described above may further comprise awater repellant, and the content of the water repellant may be 0.01 to0.30 percent by mass with respect to the total mass of the treatmentliquid composition.

According to the treatment liquid composition described above, the waterrepellant may be at least one selected from a fluorine-based waterrepellant, a silicone-based water repellant, and a paraffin wax.

According to the treatment liquid composition described above, the waterrepellant may be a resin having a melting point of 100° C. or less.

According to the treatment liquid composition described above, the clothmay be a polyester or a blend containing a polyester and a cotton.

According to the treatment liquid composition described above, the clothis a cloth having a color portion, and an L* value of the color portionmay be 80 or less.

The treatment liquid composition described above may further compriseresin particles.

The treatment liquid composition described above may further comprise anonionic surfactant, and the nonionic surfactant may be apolyoxyethylene oleyl ether.

According to the treatment liquid composition described above, thecationic compound may be a polyvalent metal salt, and the polyvalentmetal salt may be at least one selected from calcium nitrate, calciumchloride, and magnesium sulfate.

The treatment liquid composition described above may be used for ink jetpigment printing.

A set according to the present disclosure comprises: the treatmentliquid composition described above; and a pigment-printing ink jet inkcomposition which contains a pigment, resin particles, and water.

According to the set described above, the pigment-printing ink jet inkcomposition may be a white ink containing a white pigment.

An ink jet printing method according to the present disclosurecomprises: a treatment liquid composition adhesion step of adhering thetreatment liquid composition described above to the cloth.

The ink jet printing method described above may further comprise: afterthe treatment liquid composition adhesion step is performed, an inkcomposition adhesion step of adhering a pigment-printing ink jet inkcomposition which contains a pigment, resin particles, and water to aregion to which the treatment liquid composition is adhered.

A cloth according to the present disclosure is a cloth to which thetreatment liquid composition described above is adhered.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE is a schematic perspective view showing an ink jet printingapparatus according to an embodiment.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Hereinafter, embodiments of the present disclosure will be described.The following embodiments of the present disclosure are each describedas one example of the present disclosure. In addition, the presentdisclosure is not limited to the following embodiments and, inconsideration of the claims and the entire specification, may beappropriately changed and/or modified within the scope of the presentdisclosure or within the range not against the concept thereof, and atreatment liquid composition, a set, an ink jet printing method, and acloth, each of which is changed and/or modified as described above, areto be understood to be included in the technical scope of the presentdisclosure.

Treatment Liquid Composition

A treatment liquid composition (hereinafter, also simply referred to as“treatment liquid” in some cases) according to this embodiment is atreatment liquid composition which is used to be adhered to a cloth andwhich contains a cationic compound, a water-soluble resin, and water. Inaddition, the molecular weight distribution of a water-soluble componentcontained in the treatment liquid composition has a maximum peak in amolecular weight range of 28,000 to 2,800,000, and the content of awater-soluble resin having a molecular weight of 28,000 to 2,800,000 is0.6 to 5.0 percent by mass with respect to the total mass of thetreatment liquid composition.

When a printed material is formed by adhering an ink composition to acloth, the treatment liquid composition according to this embodiment ispreferably adhered in advance to a cloth functioning as a substrate ofthe printed material. As the ink composition, an ink composition whichwill be described later may be used. In particular, as the inkcomposition, when a pigment-printing ink jet ink composition is used, bythe treatment liquid composition according to this embodiment, a pigmentis likely to be retained on a surface of the cloth. Because of thecharacteristics described above, the chromogenic property of the pigmentof the printed material can be improved. Hence, the treatment liquidcomposition according to this embodiment is preferably a treatmentliquid composition for pigment printing and is more preferably atreatment liquid composition for ink jet pigment printing.

Hereinafter, individual components contained in the treatment liquidcomposition according to this embodiment will be described. In addition,as an ink composition to be used for manufacturing a printed material, apigment-printing ink jet ink composition (hereinafter, also simplyreferred to as “ink composition” in some cases) will be described by wayof example.

Cationic Compound

The treatment liquid composition according to this embodiment contains acationic compound. The cationic compound has a function to aggregatecomponents in the ink composition. That is, in the case in which aprinted material is manufactured, when the ink composition is adhered toa cloth to which the treatment liquid is adhered, the cationic compoundcontained in the treatment liquid works on particles of a pigment, resinparticles (emulsion), and the like contained in the ink composition. Asa result, the aggregation between the particles is promoted, and theparticles are suppressed from being absorbed in spaces between fibersforming the cloth or in the fibers. Hence, color development of thepigment (colorant) of the printed material can be improved. Besides theeffect described above, the cationic compound also has a function toincrease the viscosity of the ink composition. Hence, excessivepenetration of the ink composition in the cloth is suppressed, and inaddition, the generation of blurring and bleeding can also be reduced.

The functions of the cationic compound described above are derived froman action which neutralizes a surface charge of the components containedin the ink composition or an action which changes the pH of the inkcomposition. By the action as described above, the aggregation or theprecipitation of the pigment and the like in the ink composition and/orthe increase in viscosity of the ink composition can be performed.

As the cationic compound, for example, a polyvalent metal salt or acationic resin may be mentioned. Among those mentioned above, forexample, since improving the chromogenic property of the pigment andbeing preferably used for a cotton cloth and a polyester cloth, apolyvalent metal salt is preferably used. Those cationic compounds maybe used alone, or at least two types thereof may be used in combination.

The polyvalent metal salt is a water-soluble compound which contains apolyvalent metal cation having at least divalence and an anion forming asalt with the polyvalent metal cation. As the polyvalent metal cationhaving at least divalence, for example, there may be mentioned adivalent metal ion, such as Ca²⁺, Cu²⁺, Ni²⁺, Mg²⁺, Zn²⁺, or Ba²⁺, or atrivalent metal ion, such as Al³⁺, Fe³⁺, or Cr³⁺. In addition, as theanion, for example, there may be mentioned Cl⁻, I⁻, Br⁻, SO₄ ²⁻, CO₃ ²⁻,ClO₃ ⁻, NO₃ ⁻, HCOO⁻, or CH₃COO⁻. Among the polyvalent metal salts eachformed from the polyvalent metal cation and the anion in combination asdescribed above, in view of the improvement in storage stability of thetreatment liquid and the improvement in chromogenic property by thefunction to aggregate the pigment and the resin particles (emulsion), acalcium salt or a magnesium salt is preferably used. As a preferableexample of the calcium salt or the magnesium salt, there may bementioned calcium nitrate, calcium chloride, or magnesium sulfate, andat least one of those mentioned above may be used. In particular, sincethe aggregation function is high, and the chromogenic property can befurther improved, a calcium salt is more preferably used.

As the polyvalent metal salt, a hydrate thereof may also be used. As thehydrate of calcium chloride, for example, calcium chloride dihydrate mayalso be used, and as the hydrate of calcium nitrate, for example,calcium nitrate tetrahydrate may also be used. The polyvalent metalsalts may be used alone, or at least two types thereof may be used incombination. When at least two types of polyvalent metal salts are usedin combination, a calcium salt and a magnesium salt are preferably usedin combination. In the case as described above, the aggregation functionto aggregate the pigment and/or the resin particles (emulsion) is likelyto be controlled. Since the aggregation function is prevented from beingexcessively enhanced, granularity of an image of the printed materialcan be suppressed from being likely to be generated, and as a result,irregularity of color development of the image can be reduced. As themagnesium salt, magnesium sulfate is preferably used.

As the cationic compound, besides the polyvalent metal salt, a metalsalt other than the polyvalent metal salt may also be used. As the metalsalt described above, sodium sulfate or potassium sulfate may bementioned, each of which is formed using a monovalent metal cation, suchas Na⁺ or K⁺, and the anion mentioned above in combination.

As the cationic resin, for example, an urethane resin, an olefin resin,or an allylamine resin, each of which has a cationic property, may bementioned.

As the cationic urethane resin, for example, a known product or acommercially available product may be used. The cationic urethane resinmay be used after being dissolved in a solvent, such as water or anorganic solvent, or after being dispersed in the above solvent to forman emulsion. As the cationic urethane resin described above, forexample, there may be mentioned Hydran (registered trademark) CP-7010,7120, 7030, 7040, 7050, 7060, or 7610 (trade name, available from DICCorporation); Superflex (registered trademark) 600, 610, 620, 630, 640,or 650 (trade name, available from DKS Co., Ltd.); or Urethane EmulsionWBR-2120C or 2122C (trade name, manufacture by Taisei Fine Chemical Co.,Ltd.).

The cationic olefin resin is a high molecular weight compound which isderived form an olefin monomer and which has a structure, such as anethylene chain or a propylene chain, as a primary skeleton. As thecationic olefin compound, a known product or a commercially availableproduct may be used, and a cationic olefin resin dissolved in a solvent,such as water or an organic solvent, or dispersed in the solventmentioned above to form an emulsion may also be used. As the cationicolefin resin described above, for example, there may be mentioned ArrowBase (registered trademark) CB-1200 or CD-1200 (trade name, availablefrom Unitika Ltd.).

As the cationic allylamine resin, a known product may be used, and forexample, there may be mentioned a polyallylamine hydrochloride, apolyallylamineamide sulfate, an allylamine hydrochloride-diallylaminehydrochloride copolymer, an allylamine acetate-diallylamine acetatecopolymer, an allylamine hydrochloride-dimethylallylamine hydrochloridecopolymer, an allylamine-dimethylallylamine copolymer, apolydiallylamine hydrochloride, a polymethyldiallylamine hydrochloride,a polymethyldiallylamineamide sulfate, a polymethyldiallylamine acetate,a polydiallylmethylammonium chloride, a diallylamine acetate-sulfurdioxide copolymer, a diallylmethylethylammoniumethyl sulfate-sulfurdioxide copolymer, a methyldiallylamine hydrochloride-sulfur dioxidecopolymer, a diallyldimethylammonium chloride-sulfur dioxide copolymer,or a diallydimethylammonium chloride-acrylamide copolymer.

As the cationic allylamine resin described above, a commerciallyavailable product may also be used, and for example, there may bementioned PAA-HCl-01, 03, 05, 3L, 10L, PAA-H-HCL, PAA-SA, PAA-01, 03,05, 08, 15, 15C, 25, PAA-H-10C, PAA-D11-HCl, PAA-D41-HCl, PAA-D19-HCl,PAS-21CL, 22SA, 92, 92A, PAS-M-1, 1L, LA, PAS-H-1L, 5L, 10L, PAS-J-81 or81L (trade name, available from Nittobo Medical Co., Ltd.); Himoloc(registered trademark) NEO-600, Q-101, Q-311, Q-501, or Himax SC-505(trade name, available from Hymo Corporation).

In addition, besides the cationic resin and the polyvalent metal saltdescribed above, as other cationic compounds, for example, there mayalso be used a cationic surfactant, an inorganic acid, or an organicacid.

As the cationic surfactant, for example, there may be mentioned aprimary, a secondary, or a tertiary amine chloride, an alkylamine salt,a dialkylamine salt, an aliphatic amine salt, a benzalkonium salt, aquaternary ammonium salt, a quaternary alkylammonium salt, analkylpyridinium salt, a sulfonium salt, a phosphonium salt, an oniumsalt, or an imidazolinium salt. As a concrete example of the cationicsurfactant as described above, for example, there may be mentioned ahydrochloride or an acetate of laurylamine, coconut amine, or rosinamine, dodecyltrimethylammonium chloride (lauryltrimethylammoniumchloride), hexadecyltrimethylammonium chloride (cetyltrimethylammoniumchloride), benzyltributylammonium chloride, benzalkonium chloride,dimethylethyllaurylammonium ethyl sulfate, dimethylethyloctylammoniumethyl sulfate, trimethyllaurylammonium hydrochloride, cetylpyridiniumchloride, cetylpyridinium bromide, dihydroxyethyllaurylamine,decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammoniumchloride, tetradecyldimethylammonium chloride, hexadecyldimethylammoniumchloride, or octadecyldimethylammonium chloride. As the cationicsurfactants mentioned above, commercially available products may also beused.

As the inorganic acid or the organic acid, for example, there may bementioned an inorganic acid, such as sulfuric acid, hydrochloric acid,nitric acid, or phosphoric acid; an organic acid, such as a polyacrylicacid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid,ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid,tartaric acid, lactic acid, a sulfonic acid, pyrrolidone carboxylicacid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylicacid, pyridine carboxylic acid, coumaric acid, thiophene carboxylicacid, or nicotine acid; or a derivative or a salt of each of thosementioned above. Those acids may be used alone, or at least two typesthereof may be used in combination.

As another cationic compound, for example, there may be used aninorganic pigment, such as choke, kaolin, calcined clay, talc, titaniumoxide, zinc oxide, zinc sulfide, synthetic silica, aluminum hydroxide,alumina, sericite, white carbon, saponite, calcium montmorillonite,sodium montmorillonite, or bentonite; or an organic pigment, such asacrylic-based plastic pigment or an urea polymer compound.

The content of the cationic compound contained in the treatment liquidis not particularly limited and is, with respect to the total mass ofthe treatment liquid, preferably 0.1 to 40.0 percent by mass, morepreferably 2.0 to 25.0 percent by mass, further preferably 3.0 to 15.0percent by mass, and particularly preferably 5.0 to 10.0 percent bymass. Since the content of the cationic compound is set in the rangedescribed above, for example, the precipitation and/or the separation ofthe cationic compound in the treatment liquid is suppressed, and theaggregation of the pigment and/or the resin particles (emulsion) in theink composition is promoted, so that the pigment and/or the resinparticles (emulsion) are suppressed from being incorporated in thespaces between the fibers forming the cloth or in the fibers. Asdescribed above, by a sealing effect which enables the components of theink composition and the like to stay in the vicinity of the surface ofthe cloth, a phenomenon (strike-through) in which the pigment (colorant)is allowed to pass in a rear surface direction of the printed materialcan be reduced, and the chromogenic property of the pigment in theprinted material can be improved.

Water-Soluble Resin

The treatment liquid composition according to this embodiment contains awater-soluble resin. Since the water-soluble resin is contained,molecular chains of the water-soluble resin are likely to be entangledwith the fibers of the cloth, and in addition, the viscosity of thetreatment liquid composition tends to be relatively increased.Accordingly, when the treatment liquid composition is adhered to thecloth, the water-soluble resin has a function to enable the treatmentliquid composition to be likely to be retained on the surface of thecloth. In particular, since fibers of a polyester cloth have a lowhydrophilic property as compared to that of a cotton cloth, an aqueoustreatment liquid composition or an aqueous ink composition is liable tobe repelled by the fibers of the polyester cloth. Hence, the treatmentliquid composition is not likely to be fixed to the polyester cloth ascompared to that of the cotton cloth. However, since containing thewater-soluble resin composition, the treatment liquid composition can bemore preferably retained on the surface of the cloth.

In addition, in order to improve air permeability, in general, since thepolyester cloth is formed with large (loose) stitches, the inkcomposition is more likely to penetrate in the cloth in some cases.However, since containing the water-soluble resin composition, thetreatment liquid composition can be preferably retained on the surfaceof the cloth. Furthermore, when the ink composition is adhered to thecloth to which the treatment liquid composition is adhered, thewater-soluble resin is dissolved in the ink composition, and theviscosity thereof is increased. By the increase in viscosity, thefluidity of the ink composition is degraded, and the ink composition isnot likely to penetrate in the cloth and is likely to stay on thesurface of the cloth. As a result, the ink composition stays on thesurface of the cloth, so that a preferable color development can beobtained.

As the water-soluble resin, for example, there may be mentioned anonionic resin, an anionic resin, or a cationic resin. In addition, inthis specification, the cationic resin may correspond to both the abovecationic compound and water-soluble resin.

In addition, in this specification, the “water-soluble” indicates aproperty in which an object material can be dissolved in ion-exchangedwater at 20° C. at a concentration of 3 percent by mass or more, and inaddition, the object material is dissolved preferably at a concentrationof 5 percent by mass or more, more preferably at a concentration of 10percent by mass or more, and further preferably at a concentration of 25percent by mass or more.

As the water-soluble resin, at least one selected from a poly(ethyleneoxide), a carboxymethyl cellulose, a hydroxyethyl cellulose, and apoly(vinyl pyrrolidone) is preferably contained. Among those resinsmentioned above, a poly(ethylene oxide) and a poly(vinyl pyrrolidone),each of which is a nonionic resin, are preferable, and a poly(vinylpyrrolidone) is more preferable. A poly(vinyl pyrrolidone) is morelikely to be dissolved in the ink composition to increase the viscositythereof and is likely to improve the color development. In addition, apoly(vinyl pyrrolidone) has a low spinnability, and hence, a coatingproperty of the treatment liquid composition is likely to be improved.

As the poly(ethylene oxide) (hereinafter, also referred to as“polyethylene oxide” in some cases), a commercially available productmay also be used, and for example, there may be mentioned PEO(registered trademark)-1, 2, 3, 4, 8, 15, 18, 27, or 29 (trade name,available from Sumitomo Seika Chemicals Company, Limited.); or Alkox(registered trademark) L-6, L-8, L-11, E-30, E-45, E-60, E-75, E-100,E-160, E-240, E-300, R-150, R-400, or R-1000 (trade name, available fromMeisei Chemical Works, Ltd.).

In addition, the poly(ethylene oxide) is not limited to a homopolymer,and for example, a copolymer of ethylene oxide and another monomer, suchas a copolymer of ethylene oxide and propylene oxide, may also be used.

Although the weight average molecular weight of the poly(ethylene oxide)is not particularly limited, a molecular weight of 1,000 to 6,000,000 ispreferable, and a molecular weight of 10,000 to 5,500,000 is morepreferable. Since the weight average molecular weight is set in therange described above, the viscosity of the treatment liquid is likelyto be increased, and in addition, the molecular chains are likely to beentangled with the fibers of the cloth. In addition, the weight averagemolecular weight of the water-soluble resin, such as a poly(ethyleneoxide), may be measured by a known method, such as gel filtrationchromatography (GFC) or a gel permeation chromatography (GPC).

As the carboxymethyl cellulose, a commercially available product mayalso be used, and for example, there may be mentioned a sodium salt ofthe carboxymethyl cellulose, such as CMC Daicel (registered trademark)1120, 1130, 1220, 1240, 1250, or 1330 (trade name, available from DaicelFineChem Ltd.); Cellogen (registered trademark) 5A, 6A, 7A, PL-15, F-5A,F-7A, F-907A, F-815A, or PR-S (trade name, available from DKS Co.,Ltd.).

As the hydroxyethyl cellulose, a commercially available product may alsobe used, and for example, there may be mentioned HEC Daicel (registeredtrademark) SP200, SP400, SP500, SP600, SP850, SP900, SE400, SE550,SE600, SE850, SE900, or EE820 (trade name, available from DaicelFineChem Ltd.); AL-15, AG-15F, AH-15F, AV-15F, AW-15F, AX-15, SW-25F,SZ-25F, CF-G, CF-V, CF-W, CF-X, or CF-Y (trade name, available fromSumitomo Seika Chemicals Company, Limited.).

As the poly(vinyl pyrrolidone), a commercially available product mayalso be used, and for example, there may be mentioned a commerciallyavailable chemical reagent Polyvinylpyrrolidone K-30 or K-30W (tradename, available from Nippon Shokubai Co., Ltd.); PITZCOL (registeredtrademark) K-17L, K-30, K-30L, K-30AL, K-60L, K-50, or K-90, CREEJUS(registered trademark) K-30, or AIPHTACT (registered trademark) K-30PH(trade name, available from DKS Co., Ltd.); or PVP K-30, PVP K-25, orPVP K-17 (trade name, available from Ashland Inc.). In addition, thepoly(vinyl pyrrolidone) is not limited to a homopolymer, and a copolymerof vinyl pyrrolidone and another monomer may also be used.

Although the glass transition temperature of the water-soluble resindescribed above is not particularly limited, the glass transitiontemperature is preferably −80° C. to 0° C. or more preferably −80° C. to−10° C. Since the glass transition temperature of the water-solubleresin is set in the range described above, in a printed material towhich printing is performed, the texture of the substrate can bemaintained, and in addition, for example, abrasion fastness can also beimproved.

As another water-soluble resin, for example, there may also be used ahydroxypropyl methyl cellulose, a cellulose acetate, or a poly(vinylalcohol).

The content of the water-soluble resin with respect to total mass of thetreatment liquid composition is preferably 0.3 to 7.0 percent by mass,more preferably 0.5 to 6.0 percent by mass, and further preferably 0.6to 5.0 percent by mass. Since the content is set in the range describedabove, the sealing effect of the treatment liquid composition on thecloth can be obtained, and in addition, the chromogenic property of thepigment can be further improved. This effect can be more preferablyobtained when a polyester cloth having relatively large stitches isused. In addition, the cloth to which the treatment liquid compositionis adhered is suppressed from being hardened, and the texture of thecloth can be maintained.

The treatment liquid composition according to this embodiment contains0.6 to 5.0 percent by mass of a water-soluble resin having a molecularweight of 28,000 to 2,800,000 with respect to the total mass of thetreatment liquid composition. By the structure as described above, thewater-soluble resin is likely to be dissolved in the ink composition onthe cloth, and in addition, the viscosity of the ink composition ispreferably increased. By the increase in viscosity thereof, the fluidityof the ink composition is degraded, and the ink composition is notlikely to penetrate in the cloth and is likely to stay on the surface ofthe cloth. As a result, the color development of the ink composition canbe improved.

The molecular weight of the water-soluble resin is preferably 30,000 to2,700,000 and more preferably 32,000 to 2,600,000. Since the molecularweight range of the water-soluble resin is higher than the lower limit,an effect to preferably increase the viscosity of the ink compositionadhered to the cloth can be obtained, and hence, an excellentchromogenic property can be preferably obtained. Since the molecularweight range of the water-soluble resin is lower than the upper limit,the treatment liquid composition has a preferable viscosity, and at aportion to which the treatment liquid composition is adhered, thetreatment liquid composition is preferably not likely to generate ascar. In this case, the scar is generated as a coating scar which isobserved after the coating due to the different in appearance, such asthe change in hue, between the portion to which the treatment liquidcomposition is adhered and a portion to which no treatment liquidcomposition is adhered.

The treatment liquid composition according to this embodiment preferablycontains a water-soluble resin having a molecular weight of 1,000 to25,000. Since the water-soluble resin as described above is contained,the chromogenic property is further improved. Since the water-solubleresin as described above has a molecular weight smaller than thewater-soluble resin having a molecular weight of 28,000 to 2,800,000,although the effect to increase the viscosity of the ink composition islow, this water-soluble resin is rapidly dissolved in the inkcomposition, and hence, an effect to rapidly increase the viscositythereof is obtained immediately after the ink composition is adhered.Hence, when the water-soluble resin having a molecular weight of 1,000to 25,000 and the water-soluble resin having a molecular weight of28,000 to 2,800,000 are used in combination, the chromogenic propertycan be further improved. When the water-soluble resin having a molecularweight of 1,000 to 25,000 is contained, the content thereof with respectto the total mass of the treatment liquid composition is preferably 0.1to 5.0 percent by mass, more preferably 0.2 to 4.0 percent by mass, andfurther preferably 0.5 to 2.0 percent by mass.

In this specification, the molecular weight of the water-soluble resinis a molecular weight measured by the GPC method described above and isa molecular weight with respect to that of a standard product. Themeasurement of the molecular weight may be performed either on thewater-soluble resin itself or on the treatment liquid composition. Inthis case, the components contained in the treatment liquid compositionare preferably identified in advance.

In addition, in this specification, the “water-soluble” indicates theproperty described above, and the “water-soluble component” indicates acomponent having a water solubility among the components contained inthe treatment liquid composition. In more particular, although thewater-soluble component is represented by the water-soluble resindescribed above, the water-soluble component is not limited thereto, andamong the cationic compounds, a compound having a water solubility mayalso be included.

Water

The treatment liquid composition according to this embodiment containswater as a primary solvent. This water is a component which isevaporated and removed by drying performed after the treatment liquid isadhered to the substrate, such as the cloth. As the water, for example,there may be used purified water, such as ion-exchanged water,ultrafiltration water, reverse osmosis water, or distilled water, orwater, such as ultrapure water, in which ionic impurities are removed asmuch as possible. In addition, when water which is sterilized byultraviolet irradiation or addition of hydrogen peroxide is used, in thecase in which the treatment liquid is stored for a long time, thegeneration of fungi and bacteria can be suppressed. In addition, theprimary solvent of the treatment liquid composition is not limited towater, and for example, a water-soluble organic solvent may also be usedas the primary solvent.

The content of the water contained in the treatment liquid compositionwith respect to the total mass (100 percent by mass) of the treatmentliquid composition may be set, for example, to 50 percent by mass ormore, and is preferably 60 to 99 percent by mass, more preferably 70 to98 percent by mass, and further preferably 80 to 95 percent by mass.Since the content of the water is set in the range described above, theincrease in viscosity of the treatment liquid composition is suppressed,and in addition, the workability obtained when the treatment liquidcomposition is adhered to the cloth and the drying property obtainedafter the treatment liquid composition is adhered thereto can beimproved. In addition, the water of the treatment liquid includes waterwhich is used as a raw material of the treatment liquid, such as waterblended in a resin emulsion which will be described later.

Water Repellant

The treatment liquid composition according to this embodiment preferablycontains a water repellant. In this specification, the water repellantindicates an additive which is used to impart a repellent property to acloth surface to which the treatment liquid composition is adhered. Whenthe treatment liquid composition contains a water repellant, since therepellent property can be imparted to the cloth surface to which thetreatment liquid composition is adhered, an ink composition containingwater as a primary solvent is likely to stay on the surface of thecloth, and hence, the chromogenic property can be improved. Inparticular, when the water repellant is used together with thewater-soluble resin described above, during a period immediately afterthe ink composition is adhered to the generation of the sealing effectby the increase in viscosity of the water-soluble resin, the inkcomposition can be allowed to stay on the cloth surface, and hence, thechromogenic property can be further improved.

The water repellant is a compound having a hydrophilic portion and ahydrophobic portion and may be in the form of particles, and by the useof the water repellant as described above, the water repellant isselectively oriented on the surface of a coating film, so that variousfunctions, such as a water repellent property and a slip property, canbe obtained. The water repellant as described above is not particularlylimited, and for example, there may be mentioned calcium stearate,ammonium stearate, a silicone-based water repellant, a fluorine-basedwater repellant, a polyethylene wax, a paraffin wax, a carnauba wax, ora polyethylene-paraffin wax. Those water repellants mentioned above maybe used alone, or at least two types thereof may be used in combination.

Among the water repellants mentioned above, in order to more effectivelyand reliably obtain the effect of the present disclosure, the waterrepellant is preferably at least one selected from a fluorine-basedwater repellant, a silicone-based water repellant, and a paraffin waxresin. The water repellant may be in the form of an oxide or in the formof a derivative incorporating a functional group, such as a carboxylgroup. In addition, since the viscosity can be further decreased, thewater repellant is preferably in the form of resin particles (emulsion).As the type of emulsion, for example, an emulsion polymerization type, aforced emulsion type, and a self emulsion type may be mentioned. Whenthe water repellant is in the form of resin particles, for example,since the viscosity is decreased, a film forming property is improved,and even when the water repellant is added to the treatment liquidcomposition at a low concentration, the uniformity in an adhesionsurface is improved. In addition, the water repellant is not likely tobe dissolved in the ink composition, and hence, a preferable repellentproperty is likely to be obtained.

In this embodiment, the water repellant is preferably a resin having amelting point of 150° C. or less, more preferably a resin having meltingpoint 100° C. or less, and further preferably a resin having a meltingpoint of 70° C. to 100° C. Since the melting point of the waterrepellant is 150° C. or less, the film forming property obtained whenthe treatment liquid composition is adhered to the cloth is preferable,and even when the water repellant is added to the treatment liquidcomposition at a low concentration, the uniformity in the adhesionsurface is improved. In addition, since the melting point of the waterrepellant is 70° C. or more, the water repellant is not likely to bedissolved in the ink composition, and hence, a preferable repellentproperty is likely to be obtained.

As the water repellant described above, a commercially available productmay also be used, and for example, there may be mentioned AQUACER(registered trademark) 497, 537, or 539 (trade name, manufactured by BYKJapan KK, paraffin wax); SFCOAT (registered trademark) SWK-601 (tradename, manufactured by AGC SEIMI CHEMICAL CO., LTD., fluorine-based waterrepellant).

In this embodiment, the content of the water repellant with respect tothe total mass of the treatment liquid composition is preferably 0.01 to5.0 percent by mass, more preferably 0.01 to 0.30 percent by mass, andfurther preferably 0.05 to 0.10 percent by mass. Since the content ofthe water repellant is 0.01 percent by mass or more, the chromogenicproperty of the ink composition can be further improved, and since thecontent of the water repellant is 5 percent by mass or less, thegranularity of the image can be reduced, and the irregularity of colordevelopment of the image can be reduced.

Resin Particles

The treatment liquid composition according to this embodiment preferablycontains resin particles. In this specification, the resin particles arepreferably resin particles different from those of the water repellant,and as a material forming the resin particles, an urethane-based resin,a vinyl acetate-based resin, an acrylic-based resin, astyrene-acrylic-based resin, or a polyester-based resin is preferable,and at least one of those mentioned above is preferably used. By the useof the resin particles, fixability of the colorant (pigment) containedin the ink composition to the cloth can be further improved. Inaddition, as a sealing agent which suppresses the treatment liquidcomposition and/or the ink composition from excessively penetrating(infiltrating) in the cloth, the resin particles may also be used.

When the treatment liquid composition uses water as a primary solvent asis the case of this embodiment, the resin particles may be used as aresin emulsion in which the resin particles are dispersed in an aqueoussolvent. As a method for dispersing the resin particles, a forcedemulsion type using an emulsifier (surfactant) or a self emulsion typeincorporating a hydrophilic portion (hydrophilic group) in a molecularstructure of the resin particles may be used. In addition, the resinparticles may have a reactivity (cross-linking reactivity), and forexample, resin particles having an isocyanate group masked by a blockingagent in the molecular structure may also be used.

The average particle diameter of the resin particles is preferably 30 to300 nm and more preferably 40 to 100 nm. When the average particlediameter is set in the range described above, the dispersibility of theresin emulsion in the treatment liquid composition and the fixabilitythereof to the cloth can be improved. In addition, in thisspecification, the “average particle diameter” indicates a volume-basisparticle size distribution (50%) unless otherwise particularly noted.The average particle diameter is measured by a dynamic light scatteringmethod or a laser diffraction method described in JIS 28825. Inparticular, a particle size distribution meter (such as “Microtrac UPA”available from Nikkiso Co., Ltd.) using a dynamic light scatteringmethod as a measurement principle may be used.

As the resin emulsion described above, a commercially available productmay also be used. For example, as the urethane-based resin emulsion, forexample, there may be mentioned Superflex (registered trademark) 150,420, 460, 470, 500, 610, 700, 800, 870, 6E-2000, E-2500, E-4000, orR-5000 (trade name, available from DKS Co., Ltd.); Adeka Bontaita(registered trademark) HUX-290K, 380, 822, or 830 (trade name, availablefrom ADEKA Corporation); Takelac (registered trademark) W-6020, 6021,6061, 605, 635, or WS-6021 (trade name, available from Mitsui ChemicalsPolyurethanes, Inc.); Permarin (registered trademark) UA-150 (tradename, available from Sanyo Chemical Industries, Ltd.); Suncure(registered trademark) 2710 (trade name, available from NipponLubrizol); or NeoRez (registered trademark) R-940, 9637, or 9660 (tradename, available from Kusumoto Chemicals, Ltd.).

As the vinyl acetate-based resin emulsion, for example, there may bementioned Vinyblan (registered trademark) 1245L (trade name, availablefrom Nisshin Chemical Industry Co., Ltd.); Polysol (registeredtrademark) SH-502, AD-2, 10, 13, 17, 70, or 96 (trade name, availablefrom Showa Denko K.K.); or Seikadyne (registered trademark) 1900W (tradename, available from Dainichiseika Color & Chemicals Mfg. Co., Ltd.).

As the acrylic-based resin emulsion, for example, there may be mentionedVoncoat (registered trademark) AN-402, R-3310, R-3360, or 4001 (tradename, available from DIC Corporation); Polysol (registered trademark)AM-710, 920, 2300, AP-4735, AT-860, or PSASE-4210E (trade name, ShowaDenko K.K.); Saivinol (registered trademark) SK-200 (trade name,available from Saiden Chemical Industry Co., Ltd.); AE-120A (trade name,available from JSR Corporation); Vinyblan (registered trademark) 2650,2680, 2682, 2684, 2886, or 5202 (trade name, available from NisshinChemical Industry Co., Ltd.); or NK-Binder R-5HN (trade name, availablefrom Shin Nakamura Chemical Co., Ltd.).

As the styrene-acrylic-based resin emulsion, for example, there may bementioned Microgel (registered trademark) E-1002 or 5002 (trade name,available from Nippon Paint Co., Ltd.); Voncoat (registered trademark)5454 (trade name, available from DIC Corporation); Polysol (registeredtrademark) AP-7020 (trade name, available from Showa Denko K.K.);SAE1014 (trade name, available from Zeon Corporation); AE373D (tradename, available from Emulsion Technology Co., Ltd.); Joncryl (registeredtrademark) 390, 450, 511, 631, 632, 711, 734, 741, 775, 780, 790, 840,852, 1535, 7001, 7100, 7600, 7610, 7640, 7641, 74J, 352D, 352J, 537J,538J, HRC-1645J, PDX-7145, or 7630A (trade name, available from BASF);Movinyl (registered trademark) 966A or 7320 (trade name, available fromNippon Synthetic Chemical Industry Co., Ltd.).

As the polyester-based resin emulsion, for example, there may bementioned Elytel (registered trademark) KA-50715, KT-8701, 8803, 8904,9204, or 0507 (trade name, available from Unitika Ltd.); or HytecSN-2002 (trade name, available from Toho Chemical Industry Co., Ltd.).

Among the resin emulsions described above, in order to suppress areaction with a cationic polymer, a nonionic or a cationic resinemulsion is more preferably used.

When the resin particles are used for the treatment liquid composition,the content (content of the resin emulsion based on a solid component)with respect to the total mass of the treatment liquid composition ispreferably 0.1 to 20.0 percent by mass, more preferably 0.1 to 7.0percent by mass, and further preferably 0.5 to 1.0 percent by mass.Since the content of the resin particles based on the solid component isset in the range described above, while the degradation in storagestability and the increase in viscosity of the treatment liquidcomposition are suppressed, washing fastness, abrasion fastness, and thelike of the printed material can be improved.

Surfactant

To the treatment liquid composition, a surfactant may be further added.The surfactant has a function to decrease the surface tension of thetreatment liquid composition and to increase a penetration property inthe cloth. As the surfactant, for example, there may be mentioned anonionic surfactant, an anionic surfactant, a cationic surfactant, or anampholytic surfactant, and at least one of those surfactants may beused. In particular, since the function of the above cationic compoundis not likely to be disturbed, a nonionic surfactant is preferably used.

When the surfactant is added to the treatment liquid composition, thecontent of the surfactant with respect to the total mass of thetreatment liquid composition is preferably 2.0 percent by mass or less,more preferably 1.5 percent by mass or less, and further preferably 1.1percent by mass or less. Since the content of the surfactant is set inthe range described above, the surface tension of the treatment liquidcomposition is suppressed from being excessively decreased, and when thetreatment liquid composition is adhered to the cloth, the treatmentliquid composition is likely to be retained on the surface of the cloth.Accordingly, the function of the treatment liquid composition can beeasily obtained. In addition, when the surfactant is added, the lowerlimit of the content of the surfactant with respect to the total mass ofthe treatment liquid composition is preferably 0.01 percent by mass ormore, more preferably 0.05 percent by mass or more, and furtherpreferably 0.07 percent by mass or more. Since the content of thesurfactant is set in the range described above, when the treatmentliquid composition is adhered to the cloth, the wettability to the clothcan be improved.

As the fluorine-based surfactant, a commercially available product maybe used, and for example, there may be mentioned Megafac (registeredtrademark) F-479 (trade name, available from DIC Corporation) or BYK-340(trade name, available from BYK Japan KK).

Although the silicone-based surfactant is not particularly limited, apolysiloxane-based compound may be used. The polysiloxane-based compoundis not particularly limited, and for example, a polyether modifiedorganosiloxane may be mentioned. As a commercially available product ofthe polyether modified organosiloxane, for example, there may bementioned BYK-302, 306, 307, 333, 341, 345, 346, 347, or 348 (tradename, available from BYK Japan KK); or KF-351A, 352A, 353, 354L, 355A,615A, 945, 640, 642, 643, 6020, 6011, 6012, 6015, 6017, or X-22-4515(trade name, available from Shin-Etsu Chemical Co., Ltd.).

As the anionic surfactant, for example, there may be mentioned a higherfatty acid salt, a soap, an α-sulfo fatty acid methyl ester salt, analkylbenzene sulfonate, an alkyl sulfate ester salt, an alkyl ethersulfate ester salt, a monoalkyl phosphate ester salt, an α-olefinsulfonate, an alkylene naphthalene sulfonate, a naphthalene sulfonate,an alkane sulfonate, a polyoxyethylene alkyl ether sulfate, asulfosuccinate, a polyoxyalkylene glycol alkyl ether phosphate estersalt.

As the cationic surfactant, for example, there may be mentioned aquaternary ammonium salt, such as an alkyltrimethylammonium salt, adialkyldimethylammonium salt, or an alkyldimethylbenzylammonium salt, oran amine salt compound, such as a N-methylbishydroxyethylamine fattyacid ester hydrochloride. In addition, as the cationic surfactant, thecationic compound described above may also be used.

The ampholytic surfactant is not particularly limited, and for example,an amino acid compound, such as an alkylamino fatty acid salt, may bementioned.

As the nonionic surfactant, a polyoxyalkylene-based compound having thestructure represented by the following formula (1) is preferablycontained.

R⁴—O—X—H  (1)

In the formula (1), R⁴ represents a substituted or an unsubstitutedhydrocarbon group having 16 carbon atoms or more, and X represents apolyoxyethylene skeleton or a polyoxypropylene skeleton.

In addition, among the compounds each having the structure representedby the above formula (1), a compound having the structure represented bythe following formula (1-1) is also preferable.

R⁴—O—(CHR⁵—CHR⁶—O)_(m)—H  (1-1)

In the formula (1-1), R⁴ represents a substituted or an unsubstitutedhydrocarbon group having 16 carbon atoms or more, R⁵ and R⁶ eachindependently represents hydrogen or a methyl group, one of R⁵ and R⁶represents hydrogen, and m represents an integer of 2 to 20.

In the nonionic compound represented by the formula (1-1), one endterminal of a condensed chain of ethylene oxides or propylene oxides isa monoalkyl ether, and the other end terminal thereof is a hydroxidegroup. In the nonionic compound as described above, the condensed chainportion primarily has a hydrophilic property, and the alkyl group (R⁴)of the alkyl ether portion primarily has a hydrophobic property.Accordingly, this compound is able to have an activity as an emulsifier.In the compound represented by the formula (1-1), since R⁴ has 16 carbonatoms or more, a sufficient hydrophobic property is obtained, and hence,it is believed that this compound is able to function as an emulsifier.In addition, R⁴ more preferably has 18 carbon atoms or more. The upperlimit of the number of carbon atoms is preferably 20 or less.

Since the compound as described above is used, the problems of the imagequality, such as the granularity of the image and the generation of windripples, can be preferably suppressed. The reason for this is believedthat the compound represented by the formula (1) stabilizes thedispersion system in the ink and preferably suppresses the reactivitywith the cationic compound. For example, in a pigment printing ink,since a resin or the like which is the dispersion system in the inkreacts with the cationic compound, aggregation occurs, and hence,preferable chromogenic property and abrasion fastness are obtained;however, when this reaction is excessively fast, the aggregation occursbefore dots wet spread, and a granular touch may be imparted to theimage, or wind ripples may be generated in some case. In addition, whenthe ink is adhered at a low duty, the tendency described above may bemore apparently recognized. In addition, when the viscosity of thetreatment liquid composition is high, and/or when the hydrophobicproperty of the treatment liquid composition is excessively high, thewet spreadability is degraded, and the granular touch of the image ismore liable to be generated. However, it is believed that since thecompound represented by the formula (1) is contained, the reactionbetween the dispersion system in the ink and the cationic compound isappropriately suppressed, and the ink sufficiently wet spreads, so thatthe granularity of the image and the generation of wind ripples areappropriately suppressed.

As an example of the compound represented by the formula (1), forexample, there may be mentioned a polyoxyethylene stearyl ether, apolyoxyethylene oleyl ether, or a polyoxyethylene lauryl ether. As acommercially available product corresponding to the compound describedabove, Emulgen 350 or Emulgen 420 (manufactured by Kao Corporation); orNewcol 1860, Newcol 1210, or Newcol 1204 (manufactured by NipponNyukazai Co., Ltd.). Among those compounds mentioned above, as thenonionic surfactant, a polyoxyethylene oleyl ether is preferably used.

In addition, as for the nonionic compound represented by the formula(1), an HLB (Hydrophilic-Lipophilic Balance) value can be defined, andwhen the nonionic compound represented by the formula (1) is used, theHLB value thereof is preferably 12 or more, more preferably 13 or more,and further preferably 15 or more. In this case, the HLB value is an HLBvalue defined by Griffin's method. As the compound described above, forexample, there may be mentioned Emulgen 350 (polyoxyethylene stearylether, the carbon number of R⁴ of the formula (1) is 18, the HLB valueis 17.8), Emulgen 420 (polyoxyethylene oleyl ether, the carbon number ofR⁴ of the formula (1) is 18, the HLB value is 13.6), Newcol 1860(polyoxyethylene stearyl ether, the carbon number of R⁴ of the formula(1) is 18, the HLB value is 18.1), Newcol 1210 (polyoxyethylene oleylether, the carbon number of R⁴ of the formula (1) is 18, the HLB valueis 12.4), or Newcol 1204 (polyoxyethylene oleyl ether, the carbon numberof R⁴ of the formula (1) is 18, the HLB value is 7.9).

As another nonionic surfactant, for example, an acetylene glycol-basedsurfactant, a fluorine-based surfactant, or a silicone-based surfactantmay also be used.

The acetylene glycol-based surfactant is not particularly limited, andfor example, there may be mentioned2,4,7,9-tetramethyl-5-decyne-4,7-diol, an alkylene oxide adduct of2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,4-dimethyl-5-decyne-4-ol, analkylene oxide adduct of 2,4-dimethyl-5-decyne-4-ol, or an alkyleneoxide adduct of 3,6-dimethyl-4-octyne-3,6-diol,3,5-dimethyl-1-hexyne-3-ol, or 2,4-dimethyl-5-hexyne-3-ol.

As the acetylene glycol-based surfactant described above, a commerciallyavailable product may also be used. For example, there may be mentionedSurfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM,104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37,CT111, CT121, CT131, CT136, TG, GA, or DF110D (trade name, availablefrom Air Products and Chemicals, Inc.); Olfine (registered trademark) B,Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004,EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, or AE-3(trade name, available from Nisshin Chemical Industry Co., Ltd.); orAcetynol (registered trademark) E00, E00P, E40, or E100 (trade name,available from Kawaken Fine Chemicals Co., Ltd.).

The surfactants mentioned above may be used alone, or at least two typesthereof may be used in combination. In addition, among thosesurfactants, a surfactant having an HLB (Hydrophilic-Lipophilic Balance)of 13 or more is preferably used. Accordingly, when the treatment liquidcomposition is adhered, the penetration and the wet spreading thereofwith respect to the cloth can be adjusted.

As the surfactant, the nonionic surfactant is preferably used. Sincehaving a nonionic property, the function of the cationic compounddescribed above is not disturbed.

Other Components

To the treatment liquid composition, various additives, such as a pHadjuster, an antiseptic agent, a fungicide, an antioxidant, and achelating agent, and various organic solvents may be added.

The pH adjuster is not particularly limited, and for example, there maybe mentioned an organic base or an inorganic base. As the organic base,for example, an alkanolamine, such as triethanolamine, diethanolamine,monoethanolamine, or tri-iso-propanolamine, may be mentioned. As theinorganic base, for example, a strong base, which is a hydroxide of analkali metal or an alkaline earth metal, such as lithium hydroxide,potassium hydroxide, or calcium hydroxide, may be mentioned.

As the antiseptic agent and the fungicide, for example, there may bementioned sodium benzoate, sodium pentachlorophenate, sodium2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, or1,2-dibenzisothiazoline-3-one (PROXEL CRL, PROXEL BDN, PROXEL GXL,PROXEL XL-2, or PROXEL TN, trade name of Lonza). Since the antisepticagent and/or the fungicide is added to the treatment liquid composition,bacteria and/or fungi can be suppressed from being bred in the treatmentliquid composition.

The organic solvent may be added to adjust the physical properties, suchas the viscosity and the surface tension, of the treatment liquid andthe drying property of the treatment liquid composition. When theorganic solvent is added, an organic solvent to be used for the inkcomposition described below may be used.

Method for Preparing Treatment Liquid Composition

The treatment liquid composition may be prepared in such a way thatafter the individual components described above are mixed together in anarbitrary order, if needed, the mixture thus obtained is filtrated toremove impurities and foreign materials. As a method for mixing theindividual components, there may be used a method in which the materials(components) are sequentially charged in a container equipped with astirring device, such as a mechanical stirrer or a magnetic stirrer,followed by stirring and mixing. As a filtration method, for example,centrifugal filtration or filter filtration may be used.

Physical Properties of Treatment Liquid Composition

The physical properties of the treatment liquid composition arearbitrarily adjusted in accordance with the type of cloth, the method(coating method) to adhere the treatment liquid composition to thecloth, and the like. The method for coating the treatment liquidcomposition will be described below.

The viscosity of the treatment liquid at 20° C. is not particularlylimited, and for example, the viscosity thereof is set to preferably 0.5to 100 mPa·s (millipascal·second), more preferably 1 to 50 mPa·s, andfurther preferably 1.5 to mPa·s. Since the viscosity of the treatmentliquid composition is set in the range described above, when thetreatment liquid composition is adhered to the cloth, the coatingproperty, such as the spreadability, of the treatment liquid can beimproved.

In addition, when an ink jet method is used as the coating method, theviscosity of the treatment liquid at 20° C. is set to preferably 0.5 to15 mPa·s, more preferably 1 to 5 mPa·s, and further preferably 1.5 to3.6 mPa·s. Since the viscosity of the treatment liquid composition forthe ink jet method is set in the range described above, an ejectionstability of the treatment liquid ejected from an ink jet head isimproved, and in addition, the time of a step of adhering the treatmentliquid can be decreased.

The viscosity of the treatment liquid composition is measured, forexample, using a viscoelastic tester MCR-301 (manufactured by AntonPaar). In particular, the measurement may be performed in such a waythat the temperature of the treatment liquid is controlled at 20° C.,the shear rate is increased from 0.01 s⁻¹ to 1.00 s⁻¹, and the viscosityat a shear rate of 0.10 s⁻¹ is read.

The surface tension of the treatment liquid composition at 25° C. is,for example, set to preferably 30 to 60 mN/m and more preferably 35 to50 mN/m. Since the surface tension of the treatment liquid compositionat 25° C. is set in the range described above, when the treatment liquidcomposition is adhered to the cloth, the wettability to the cloth isimproved, and in addition, the treatment liquid composition can belikely to be retained on the surface of the cloth.

The surface tension of the treatment liquid may be measured, forexample, using an automatic surface tension meter CBVP-Z (available fromKyowa Interface Science Co., Ltd.). In particular, the measurement maybe performed in such a way that in an environment at 25° C., the surfacetension is read when a platinum plate is wetted with the treatmentliquid.

Molecular Weight Distribution of Water-Soluble Component

The molecular weight distribution of the water-soluble componentcontained in the treatment liquid composition according to thisembodiment has a maximum peak in a molecular weight range of 28,000 to2,800,000. Accordingly, the water-soluble component is likely to bedissolved in the ink composition on the cloth, and in addition, theviscosity of the ink composition is preferably increased. By theincrease in viscosity, since the fluidity of the ink composition isdegraded, the ink composition is not likely to penetrate in the clothand is likely to stay on the surface thereof. As a result, a preferablecolor development can be obtained by the ink composition.

The molecular weight distribution of the water-soluble componentpreferably has a maximum peak in a molecular weight range of 30,000 to2,700,000 and more preferably has a maximum peak in a molecular weightrange of 32,000 to 2,600,000. Since the molecular weight of thewater-soluble component is higher than the lower limit, an effect topreferably increase the viscosity of the ink composition is obtained,and an excellent chromogenic property can be preferably obtained. Sincethe molecular weight of the water-soluble component is lower than theupper limit, the viscosity of the treatment liquid composition ispreferable, and a coating scar of the treatment liquid composition ispreferably not likely to be generated at a portion to which thetreatment liquid composition is adhered.

Furthermore, the molecular weight distribution of the water-solublecomponent contained in the treatment liquid composition according tothis embodiment also preferably has a maximum peak in a molecular weightrange of 1,000 to 25,000, and the ratio of a peak area of a molecularweight of 28,000 to 2,800,000 to a peak area of a molecular weight of1,000 to 25,000 is preferably 1:5 to 5:1. Accordingly, the chromogenicproperty is further improved. Since there is the peak in the rangehaving a molecular weight smaller than that of the above molecularweight distribution (28,000 to 2,800,000), although the effect toincrease the viscosity of the ink composition is low, the water-solublecomponent is more rapidly dissolved in the ink composition, and hence,an effect to increase the viscosity of the ink composition can beobtained immediately after ink composition is adhered. Hence, apreferable chromogenic property can be obtained.

In addition, since the ratio of the peak area having a molecular weightof 28,000 to U.S. Pat. No. 2,800,000 to the peak area having a molecularweight of 1,000 to 25,000 is 1:5 to 5:1, the viscosity of the treatmentliquid composition is preferable. In addition, the rate of dissolutionof the treatment liquid composition in the ink composition and theviscosity thereof after the dissolution are preferable, and hence, apreferable chromogenic property can be obtained. The molecular weightdistribution preferably has a maximum peak in a molecular weight rangeof 1,200 to 22,000 and more preferably has a maximum peak in a molecularweight range of 1,500 to 21,000. In addition, the ratio of the peak areahaving a molecular weight of 28,000 to U.S. Pat. No. 2,800,000 to thepeak area having a molecular weight of 1,000 to 25,000 is morepreferably 1:4 to 4:1 and further preferably 1:3 to 3:1.

In addition, in the molecular weight distribution described above, thepresence or absence of the maximum peak and the peak area may beobtained by the GPC method described above (also called a size-exclusionchromatography (SEC) method).

Ink Composition

Next, an ink composition will be described which is used to manufacturea printed material and which is to be printed on a cloth to which thetreatment liquid composition according to this embodiment is adhered.The ink composition according to this embodiment is preferably anaqueous pigment ink for ink jet printing. Since the number of types ofcloths to which the pigment ink can be applied is large, the pigment inkis more preferable than a dye ink. On the other hand, since penetratingin the cloth, the pigment ink is not likely to obtain the chromogenicproperty in some cases; however, when the treatment liquid compositionof the present disclosure is used, the chromogenic property can beimproved. In addition, as a printing method, since ink jet printing byan ink jet method is used, compared to related analog printing, forexample, a highly fine image can be manufactured while the manufacturingcost thereof is reduced.

The ink composition to be used in this embodiment is a pigment-printingink jet ink composition (hereinafter, simply referred to as “inkcomposition” in some cases) which contains a pigment, resin particles,and water. The ink composition used in this embodiment may form a settogether with the treatment liquid composition according to thisembodiment described above.

In addition, in the set, a white ink (white pigment-printing ink jet inkcomposition) containing a white pigment as the pigment is preferablyincluded. In addition, in the set described above, besides the whiteink, a color ink (color pigment-printing ink jet ink composition)containing a color pigment is preferably contained. In the casedescribed above, in the ink jet pigment printing method which will bedescribed later, dual-layer printing in which color printing isperformed on a white underlayer can be performed. Hereinafter, first,components contained in the ink composition according to this embodimentwill be described.

Colorant

The ink composition according to this embodiment uses a pigment as acolorant. Since the pigment is used as the colorant, compared to thecase in which a dye is used, steps, such as a dyeing step and a washingstep, can be simplified.

As the pigment, known organic pigments and inorganic pigments may beused. As the organic pigment, for example, there may be mentioned an azopigment, such as an azo lake pigment, an insoluble azo pigment, acondensed azo pigment, or a chelate azo pigment; a polycyclic pigment,such as a phthalocyanine pigment, a perylene pigment, a perinonepigment, an anthraquinone pigment, a quinacridone pigment, a dioxazinepigment, a thioindigo pigment, an isoindolinone pigment, an isoindolinepigment, a quinophthalone pigment, or diketopyrrolopyrrole pigment; adye chelate pigment, such as a basic dye lake or an acidic dye lake; anitro pigment, a nitroso pigment, an aniline black, or a daylightfluorescent pigment. As the inorganic pigment, for example, there may bementioned a metal oxide pigment, such as titanium dioxide, zinc oxide,or chromium oxide, or a carbon black. In addition, a glitter pigment,such as a pearl pigment or a metallic pigment, may also be used.

As the pigments mentioned above, for example, as a pigment for blackpigment ink, C.I. (Colour Index Generic Name) Pigment Black 1, 7, or 11may be mentioned. Among those mentioned above, for the ink jet printing,a carbon black base (C.I. Pigment Black 7) which has a relatively lowspecific gravity and which is not likely to precipitate in an aqueousmedium is preferable.

For the color pigment ink (color ink), for example, there may bementioned C.I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42,53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120,138, 153, 155, or 180; C.I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38,48:2 (Permanent Red 2B (Ba)), 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4,49:1, 52:2, 53:1, 57:1, 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101, 104,105, 106, 108, 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177,178, 179, 185, 190, 193, 209, or 219; C.I. Pigment Violet 19 or 23; C.I.Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 56, 60,or 63; C.I. Pigment Green 1, 4, 7, 8, 10, 17, 18, or 36. The averageparticle diameter of the pigment mentioned above is preferably 5 μm orless, more preferably 0.3 μm or less, and further preferably in a rangeof 0.01 to 0.15 μm. Since the average particle diameter of the pigmentis set in the range described above, the ejection stability of the inkcomposition ejected from the ink jet head can be secured, and inaddition, the chromogenic property of the pigment in the printedmaterial can be improved.

Since the chromogenic property of the pigment is improved, the treatmentliquid composition according to this embodiment is more preferably usedto print a white ink containing a white pigment. In particular, forexample, when a color image is printed on a color cloth colored inadvance, a method in which a white ink is first printed to form anunderlayer may be mentioned. This method is performed in order tosuppress the influence of the color (color of the substrate) of thecloth on a color image to be printed and to improve the colordevelopment thereof. That is, when the treatment liquid compositionaccording to this embodiment and the white ink are used together, anunderlayer having a shielding property which is improved by thechromogenic property of the white pigment is formed, and regardless ofthe color of the substrate, for example, an image having a desired colortone may be printed.

As the white pigment for white ink, for example, there may be mentionedC.I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixtureof zinc sulfide and barium sulfate), 6 (titanium dioxide), 6:1 (titaniumdioxide containing another metal oxide), 7 (zinc sulfide), 18 (calciumcarbonate), 19 (clay), 20 (mica titanium), 21 (barium sulfate),(plaster), 26 (magnesium oxide.silicon dioxide), 27 (silicon dioxide),or 28 (anhydrous calcium silicate). Among those mentioned above, C.I.Pigment White 6 having excellent chromogenic property, shieldingproperty, and the like is preferably used.

The average particle diameter of the white pigment is preferably 100 to450 more preferably 200 to 400 and further preferably 250 to 380 μm.Since the average particle diameter of the white pigment is set in therange described above, the ejection stability of the white ink ejectedfrom the ink jet head can be secured, and in addition, the shieldingproperty for the color of the cloth substrate can be improved.

For the measurement of the average particle diameter of the pigment, amethod similar to that of the average particle diameter of the resinparticles described above may also be used.

When the pigment is used, the content thereof is not particularlylimited, and for example, the content with respect to the total mass ofthe pigment ink is preferably set to 0.1 to 50.0 percent by mass, morepreferably set to 1.0 to 20.0 percent by mass, and further preferablyset to 1.0 to 15.0 percent by mass. Since the content of the pigment isset in the range described above, in the printed material in whichprinting is performed, the chromogenic property of the pigment can besecured, and in addition, the increase in viscosity of the inkcomposition and the generation of clogging in the ink jet head can besuppressed.

The pigments mentioned above may be used alone, or at least two typesthereof may be used in combination. In order to improve thedispersibility of the pigment in the ink composition, a surfacetreatment is preferably performed on the pigment, or a dispersant ispreferably blended in the ink composition. The surface treatment of thepigment is a method in which by a physical treatment or a chemicaltreatment, a hydrophilic group, such as a carboxyl group or a sulfogroup, is incorporated on the particle surface of the pigment. By thesurface treatment of the pigment, the pigment can be dispersed in anaqueous medium, such as water.

The dispersant used for the aqueous medium has a function in which ahydrophobic portion (hydrophobic group) in the molecular structure isadsorbed on the particle surface of the pigment and a hydrophilicportion (hydrophilic group) is oriented at a medium side. By thefunction described above, the pigment can be dispersed in the aqueousmedium. As the dispersant, known surfactants and high molecular weightmaterials may be used. In addition, a method in which the dispersibilityis imparted by covering the pigment particles with a high molecularweight compound may also be used. As a method for covering the pigmentparticles, for example, an acid deposition method, a phase transferemulsification method, or a mini-emulsion polymerization method may beused.

Water

The ink composition used in this embodiment is preferably an aqueousink. When an aqueous ink composition is used, water is a primary solventof the ink composition according to this embodiment. When the inkcomposition is adhered, water is evaporated and removed from the clothby drying. As the water, water similar to that used for the treatmentliquid composition described above may also be used. The content of thewater contained in the ink composition with respect to the total mass ofthe ink composition is, for example, 30 to 90 percent by mass,preferably 40 to 85 percent by mass, and more preferably 50 to 80percent by mass. Since the content of the water is set in the rangedescribed above, the increase in viscosity of the ink composition can besuppressed. In addition, in this specification, the “aqueous ink”indicates an ink composition, the water content of which is 30 percentby mass or more with respect to the total mass of the ink composition.

Organic Solvent

To the ink composition, an organic solvent may be added. By the additionof the organic solvent, the physical properties, such as the viscosityand the surface tension, and the behaviors, such as drying andpenetration, observed when the ink composition is adhered to the clothcan be adjusted. As the organic solvent, for example, there may bementioned a 2-pyrrolidone, a 1,2-alkanediol, a polyvalent alcohol, or aglycol ether. Those organic solvents may be used alone, or at least twotypes thereof may be used in combination.

The 2-pyrrolidone indicates a compound having a 2-pyrrolidone skeleton.As the 2-pyrrolidone, for example, besides a 2-pyrrolidone having nosubstituent, a compound having a substituent, such asN-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or N-vinyl-2-pyrrolidone,may be mentioned. As the substituent in the 2-pyrrolidoen skeleton, anorganic group, such as a saturated or an unsaturated hydrocarbon group,having 1 to 5 carbon atoms is preferable. Among those compoundsmentioned above, 2-pyrrolidone, which has an excellent storage stabilityof the ink composition and an excellent effect to suppress thegeneration of aggregates, is more preferably used.

As the 1,2-alkanediol, for example, there may be mentioned1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, or1,2-octanediol. The 1,2-alkanediol improves the wettability of the inkcomposition to the cloth and has an excellent function to uniformly wetthe cloth. Hence, an image suppressing the generation of blurring can beformed. The content of the 1,2-alkanediol to be added is preferably 1 to20 percent by mass with respect to the total mass of the inkcomposition.

As the polyvalent alcohol, for example, there may be mentioned ethyleneglycol, diethylene glycol, triethylene glycol, propylene glycol,dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,3-pentanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,3-butanediol,3-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,2-methyl-2,4-pentanediol, or glycerin. By the addition of the polyvalentalcohol to the ink composition, drying and solidification of the inkcomposition in an ejection nozzle of the ink jet head are suppressed,and the clogging of the ejection nozzle and the ejection defect can besuppressed. The content of the polyvalent alcohol is preferably 2 to 20percent by mass with respect to the total mass of the ink composition.In addition, a solid polyvalent alcohol at 20° C. also has a functionsimilar to that of the polyvalent alcohol used as the organic solventand may also be used in a manner similar to that described above. As thesolid polyvalent alcohol at 20° C., for example, trimethylol propane maybe mentioned.

As the glycol ether, for example, an alkylene glycol monoether or analkylene glycol diether may be mentioned.

As the alkylene glycol monoether, for example, there may be mentionedethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether,ethylene glycol monohexyl ether, ethylene glycol monophenyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,diethylene glycol monobutyl ether, diethylene glycol monohexyl ether,triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,triethylene glycol monobutyl ether (butyl triglycol), tetraethyleneglycol monomethyl ether, tetraethylene glycol monoethyl ether, propyleneglycol monomethyl ether, propylene glycol monoethyl ether, dipropyleneglycol monomethyl ether, or dipropylene glycol monoethyl ether.

As the alkylene glycol diether, for example, there may be mentionedethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethyleneglycol dibutyl ether, diethylene glycol dimethyl ether, diethyleneglycol diethyl ether, diethylene glycol methyl ethyl ether, diethyleneglycol dibutyl ether, diethylene glycol butyl methyl ether, triethyleneglycol dimethyl ether, triethylene glycol diethyl ether, triethyleneglycol dibutyl ether, triethylene glycol butyl methyl ether,tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether,tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether,propylene glycol diethyl ether, dipropylene glycol dimethyl ether, ordipropylene glycol diethyl ether.

By the addition of the glycol ether to the ink composition, thewettability and the penetration rate to the cloth (such as a polyestercloth) may be adjusted. The content of the glycol ether added to the inkcomposition is preferably 0.05 to 6 percent by mass with respect to thetotal mass of the ink composition.

As the organic solvent described above, a plurality of organic solventsmay be used in combination. In this case, the content of the total ofthe organic solvents in the ink composition is, with respect to thetotal mass of the ink composition, preferably 0.2 to 30 percent by mass,preferably 0.4 to 20 percent by mass, more preferably 0.5 to 15 percentby mass, and further preferably 0.7 to 10 percent by mass. Since thecontent of the total of the organic solvents is set in the rangedescribed above, the suppression of the increase in viscosity of the inkcomposition, the adjustment of behaviors (penetration and wet spreading)in the cloth, and the reduction in ejection defects of the ink jet headcan be performed.

Surfactant

To the ink composition, a surfactant may also be added. The surfactanthas a function to decrease the surface tension of the ink compositionand to increase the penetration property in a polyester cloth. As thesurfactant, for example, a nonionic surfactant, an anionic surfactant, acationic surfactant, or an ampholytic surfactant may be mentioned, andat least one of those surfactants may be used. As the surfactantdescribed above, a surfactant similar to that used for the treatmentliquid composition described above may be used.

The content of the surfactant added to the ink composition with respectto the total mass of the ink composition is 0.01 to 3.00 percent bymass, preferably 0.05 to 2.00 percent by mass, more preferably 0.10 to1.00 percent by mass, and further preferably 0.20 to 0.50 percent bymass. Since the content of the surfactant is set in the range describedabove, the ejection stability from the ink jet head is secured whilefoaming is suppressed, and in addition, the ink composition is likely tobe brought into contact with the components of the treatment liquidcomposition adhered to the cloth, so that, for example, the function ofthe treatment liquid composition to aggregate the ink composition isenhanced.

Chelating Agent

To the ink composition, a chelating agent may also be added. Thechelating agent has a function to trap metal ions and the like. Hence,when the chelating agent is used for the ink composition, metals ionscontained in the ink composition as impurities or mixed in from a memberin contact with the ink composition are trapped, and hence, thegeneration of foreign materials derived from the metal ions can bereduced. As the chelating agent, for example, there may be mentioned anethylenediaminetetraacetatic acid (EDTA) salt, a nitrilotriacetate, ahexametaphosphate, a pyrophosphate, or a metaphosphate.

pH Adjuster

To the ink composition, a pH adjuster may also be added. The pH adjusteris not particularly limited, and for example, an organic base or aninorganic base may be mentioned. By the use of at least one of those pHadjusters, the pH of the ink composition is preferably adjusted in a pHrange of 7.5 to 10.5. Since the pH of the ink composition is set in therange described above, for example, in an ink jet printing apparatusincluding an ink jet head, a member, such as an ink repellent film, issuppressed from being corroded.

As the organic base, for example, an alkanolamine, such astriethanolamine, diethanolamine, monoethanolamine, ortri-iso-propanolamine, may be mentioned. In this case, when the pH ofthe ink composition is set in the range described above by using atleast one of those organic bases, a relatively large amount of the pHadjuster is required. In particular, for example, the content thereofwith respect to the total mass of the ink composition is approximately0.1 to 3 percent by mass.

As the inorganic base, for example, a strong base, which is a hydroxideof an alkali metal or an alkaline earth metal, such as lithiumhydroxide, potassium hydroxide, or calcium hydroxide, may be used. Whenthe pH of the ink composition is set in the range described above byusing at least one of those inorganic bases, for example, the contentthereof with respect to the total mass of the ink composition may be setto approximately 0.03 to 0.15 percent by mass. As described above, forexample, since the addition amount of the inorganic base is small ascompared to that of the organic base, and since the inorganic base hasno odor unlike the organic base, the inorganic base is preferably used.

Resin Particles

The ink composition preferably contains resin particles. Since the resinparticles are contained, the washing fastness and the abrasion fastnessof the printed material are further improved. As the resin particles, aresin emulsion similar to that used for the treatment liquid compositiondescribed above may also be used.

The content of the resin particles with respect to the total mass of theink composition is preferably 2 to 40 percent by mass on a solidcomponent basis, more preferably 4 to 35 percent by mass, and furtherpreferably 5 to 33 percent by mass. Since the content of the resinparticles is set in the range described above, the generation ofclogging of the nozzle of the ink jet head is reduced, and in addition,the washing fastness and the abrasion fastness of the printed materialcan be further improved.

Other Components

In the ink composition, as other components, various additives, such asa fungicide, an antiseptic agent, each of which is similar to that usedfor the treatment liquid, and an antioxidant may also be appropriatelyused.

Preparation of Ink Composition

The ink composition according to this embodiment may be prepared in sucha way that after the components described above are mixed together in anarbitrary order to form a mixture, if needed, impurities and foreignmaterials are removed by filtration or the like. As a method for mixingthe individual components, there may be used a method in which thematerials (components) are sequentially charged in a container equippedwith a stirring device, such as a mechanical stirrer or a magneticstirrer, followed by stirring and mixing. As a filtration method, forexample, centrifugal filtration or filter filtration may be used.

Physical Properties of Ink Composition

The viscosity of the ink composition at 20° C. is preferably 2 to 15mPa·s, more preferably 2 to 5 mPa·s, and further preferably 2 to 3.6mPa·s. Since the viscosity of the ink composition is set in the rangedescribed above, the ejection stability and the ejection amount of theink composition from the ink jet head can be secured. In addition, inthe case in which the viscosity of the ink composition is out of therange described above, when the ejection conditions of the inkcomposition in the ink jet head and/or the type of ink jet head ischanged, the ejection stability of the ink composition may be secured insome cases, and for example, under temperature adjustment conditions,the ejection stability may be secured up to a viscosity of 22 mP·s insome cases. The viscosity of the ink composition may be measured by amethod similar to that for the treatment liquid composition describedabove.

The surface tension of the ink composition at 25° C. is set to, forexample, preferably 10 to 40 mN/m and more preferably 25 to 40 mN/m.Since the surface tension of the ink composition at 25° C. is set in therange described above, when printing is performed, the wettability tothe cloth and the contact with the components of the treatment liquidcomposition can be promoted. The viscosity and the surface tension ofthe ink composition each may also be measured by a method similar thatfor the treatment liquid composition described above.

Printing Apparatus Printer

Next, a printing apparatus according to this embodiment will bedescribed with reference to FIGURE. The printing apparatus according tothis embodiment is preferably an ink jet printing apparatus. The ink jetprinting apparatus is an apparatus configured so that by an ink jetmethod to eject fine liquid droplets of an ink composition, the liquiddroplets are landed on a cloth for printing. FIG. 1s a schematicperspective view showing the ink jet printing apparatus according tothis embodiment. In this embodiment, as the ink jet printing apparatus,an on-carriage type printer in which ink cartridges are mounted on acarriage will be described by way of example. In addition, in FIGURE, inorder to facilitate the recognition of the presence of each member, thescale reduction of the member is made different from that of the actualmember.

A printer 1 of this embodiment is a so-called serial printer. The serialprinter is a printer configured so that an ink jet head is mounted on acarriage which moves in a predetermined direction, and as the carriagemoves, the ink jet head performs printing while moving.

As shown in FIGURE, the printer 1 includes an ink jet head 3, carriage4, a main scanning mechanism 5, a platen roller 6, and a control portion(not shown) controlling the operation of the entire printer 1. Thecarriage 4 mounts the ink jet head 3 and also detachably mounts inkcartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f, each of which receives anink composition to be supplied to the ink jet head 3.

The main scanning mechanism 5 includes a timing belt 8 coupled to thecarriage 4, a motor 9 driving the timing belt 8, and a guide shaft 10.The guide shaft 10 functions as a support member of the carriage 4 andis provided in a scanning direction (main scanning direction) of thecarriage 4. The carriage 4 is driven by the motor 9 with the timing belt8 interposed therebetween and is able to reciprocally move along theguide shaft 10. Accordingly, the main scanning mechanism 5 has afunction to reciprocally transport the carriage 4 in the main scanningdirection.

The platen roller 6 functions to transport a cloth 2 to be printed in asub-scanning direction (length direction of the cloth 2) orthogonal tothe main scanning direction. Hence, the cloth 2 is transported in thesub-scanning direction. In addition, the carriage 4 on which the ink jethead 3 is mounted is able to reciprocally move in the main scanningdirection which approximately coincides with the width direction of thecloth 2, and the ink jet head 3 is able to relatively scan the cloth 2in the main scanning direction and the sub-scanning direction.

The ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f are independent 6ink cartridges. In the ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f,the ink composition according to this embodiment may be received. In theink cartridges described above, ink compositions having colors, such asblack, cyan, magenta, yellow, white, and orange, are respectivelyreceived and can be used in an arbitrary combination. In FIGURE,although the number of the ink cartridges is 6, the number is notlimited thereto. On a bottom portion of each of the ink cartridges 7 a,7 b, 7 c, 7 d, 7 e, and 7 f, a supply port (not shown) is provided tosupply the ink composition received in each ink cartridge to the ink jethead 3.

The ink jet head 3 includes a nozzle surface (not shown) in a surfacefacing the cloth 2. Along the nozzle surface, nozzle lines formed ofnozzles (not shown) are separately disposed so as to corresponding tothe respective ink compositions. The ink compositions are supplied tothe ink jet head 3 from the respective ink cartridges and are ejected inthe form of liquid droplets by actuators (not shown) in the ink jet head3. The liquid droplets of the ink composition thus ejected are landed onthe cloth 2 to form an image, a text, a pattern, a color, or the like ina printing region of the cloth 2.

In this case, in the ink jet head 3, as the actuator (driving unit),although a piezoelectric element is used, the actuator is not limitedthereto. For example, an electromechanical conversion element whichdisplaces a vibration plate used as the actuator by electrostaticadsorption or an electrothermal conversion element which ejects the inkcomposition in the form of liquid droplets by foams generated byheating.

In addition, in this embodiment, as the ink jet printing apparatus,although the on-carriage type printer 1 is described by way of example,the ink jet printing apparatus is not limited thereto. For example, anoff-carriage type printer in which an ink container, such as an inkcartridge, is not mounted on a carriage may also be used. In addition,the ink jet printing apparatus used in the present disclosure is notlimited to the serial printer described above, and there may be used aline head printer in which the ink jet head is formed to have a widthequivalent to or large than the width of the cloth 2 and in whichprinting is performed without moving the ink jet head.

Cloth

As the form of the cloth 2 according to this embodiment, for example,textiles, clothes, or other clothing ornaments may be mentioned. Thetextiles include a woven fabric, a knitted fabric, a non-woven cloth,and the like. Besides sewn products, such as a T shirt, a handkerchief,a scarf, a towel, a handbag, and a fabric bag, and furniture products,such as a curtain, a sheet, a bedspread, and wallpaper, the clothes andthe clothing ornaments also include cloths before and after cutting tobe used as components to be sewn. As the form of those products, forexample, there may be mentioned a long product wound to have a rollshape, a product cut to have a predetermined size, a product having aproduct shape.

The cloth 2 is preferably a polyester cloth containing a polyester.Since fibers of the polyester cloth have a lower hydrophilic propertythan that of cotton, an aqueous pre-treatment agent and/or an aqueousink composition is liable to be repelled by the polyester fibers and isnot likely to be fixed thereto as compared to the case of a cottoncloth. In addition, since the polyester cloth is formed with large(loose) stitches so as to improve the air permeability, the inkcomposition is more liable to penetrate in the cloth in some cases.Hence, by the polyester cloth, it has been difficult to obtain apreferable chromogenic property; however, according to the treatmentliquid composition of the present disclosure, even by the polyestercloth, a preferable chromogenic property can be obtained.

The polyester cloth contains polyester fibers and indicates a clothformed from, as a forming material, polyester fibers themselves or blendfibers containing polyester fibers and other fibers. As the otherfibers, for example, there may be mentioned natural fibers of cotton,silk, hemp, wool, or the like; or synthetic fibers of a polypropylene,an acetate, a triacetate, a polyamide, a polyurethane, a poly(lacticacid), or the like. As the polyester cloth, a cloth formed from, as aforming material, polyester fibers themselves or blend fibers containinga polyester and a cotton is preferable.

The weight per unit area of the cloth 2 is 1.0 to 10.0 ounces,preferably 2.0 to 9.0 ounces, more preferably 3.0 to 8.0 ounces, andfurther preferably 4.0 to 7.0 ounces. By the treatment liquid accordingto this embodiment, since the component, such as the cationic compound,of the treatment liquid composition is retained on a surface side of thecloth 2 in the range of the weight per unit area described above, thechromogenic property can be improved as compared to that in the past. Inaddition, the treatment liquid composition may also be applied to aplurality of clothes having different weights per unit area.

The cloth 2 is preferably a polyester cloth colored with a dye inadvance. Since the chromogenic property is improved by the treatmentliquid composition according to this embodiment, the substrate color isshielded, and hence, the interference by the substrate color can besuppressed. That is, the treatment liquid composition can be preferablyapplied to a polyester cloth having a color portion colored in advance.In addition, since the substrate colored in advance is used, a printedmaterial (product) in accordance with the preference of a customer maybe provided.

As the cloth colored in advance, a color portion preferably has an L*value of 80 or less. In this case, although the L* value can be measuredusing a known colorimeter, for example, the measurement may be performedusing Spectrolino (available from Gretag Macbeth A.G.). When the inkcomposition is adhered to a cloth having an L* value of 80 or less, thecolor of the cloth itself may be observed through an adhesion portion ofthe ink composition in some cases, and hence, in order to prevent thecase described above, the ink composition is required to have a higherchromogenic property (shielding property). Furthermore, in the case of apolyester cloth, as described above, it has been difficult to obtain apreferable chromogenic property.

On the other hand, according to the present disclosure, since the inkcomposition is preferably allowed to stay on the surface of the cloth bythe treatment liquid composition according to the present disclosure,the chromogenic property is improved, and the ink composition can bepreferably applied to a cloth having an L* value of 80 or less. The L*value may be 75 or less and may also be 70 or less. According to thetreatment liquid composition of the present disclosure, even when acloth having a deep color as described above is used, the chromogenicproperty can be improved, and hence, the ink composition can bepreferably applied.

As a dye which dyes the cloth 2 in advance, for example, a water-solubledye, such as an acidic dye or a basic dye, a dispersive dye to be usedwith a dispersant (surfactant), or a reactive dye may be mentioned.Since the cloth 2 contains polyester fibers, a dispersive dye suitablefor dyeing polyester fibers is preferably used. As the dispersive dyesuitable for dyeing polyester fibers, a compound which is not likely tobe sublimated in a heating step which will be described later ispreferable. As the dispersive dye described above, a known dye may beused. In addition, the dispersive dye is preferably used together with adispersant. As the dispersant, a known dispersant, such as a surfactant,may be used.

As a method to dye the cloth 2 with a dye, in accordance with a materialforming the cloth 2 and the form thereof, a known method may be used.

Ink Jet Printing Method

Next, an ink jet printing method according to this embodiment will bedescribed. The ink jet printing method according to this embodimentincludes a treatment liquid composition adhesion step in which atreatment liquid composition is adhered to a cloth. In addition, afterthe treatment liquid composition adhesion step is performed, an inkcomposition adhesion step is performed such that a pigment-printing inkjet ink composition which contains a pigment, resin particles, and wateris adhered to a region to which the treatment liquid composition isadhered.

Treatment Liquid Composition Adhesion Step

In the treatment liquid composition adhesion step, in order to improvethe color development of a pigment in a printed material, before the inkcomposition is adhered to the cloth, a treatment liquid compositionwhich aggregates the components of the ink composition is adhered to thecloth. That is, the cloth 2 is preferably a cloth to which the treatmentliquid composition according to this embodiment is adhered.

As the treatment liquid composition to be adhered to the cloth, thetreatment liquid composition described above is used. The adhesionamount of the treatment liquid composition is set to, for example,preferably 0.02 to 0.5 g/cm² and more preferably 0.02 to 0.24 g/cm².Since the adhesion amount of the treatment liquid composition is set inthe range described above, the treatment liquid composition is likely tobe uniformly adhered to the cloth, and aggregate irregularity of animage in the printed material can be suppressed, and hence, the colordevelopment can be improved.

In addition, in the treatment liquid composition adhesion step, when thetreatment liquid composition contains a polyvalent metal salt, theadhesion amount of the polyvalent metal salt contained in the treatmentliquid composition adhered to the cloth is set to preferably 1.6 to 6μmol/cm² and more preferably 2 to 5 μmol/cm². Since the treatment liquidcomposition is adhered so that the adhesion amount of the polyvalentmetal salt is 1.6 μmol/cm² or more, the chromogenic property of theimage in the printed material is improved. In addition, since thetreatment liquid composition is adhered so that the adhesion amount ofthe polyvalent metal salt is 6 μmol/cm² or less, the abrasion fastnessof the image is improved.

As a method to adhere the treatment liquid composition to the cloth, forexample, a method (dipping coating) in which the cloth is dipped in thetreatment liquid composition, a method (roller coating) in which thetreatment liquid composition is coated using a roller coater or thelike, a method (spray coating) in which the treatment liquid compositionis sprayed by a spray device or the like, or a method (ink jet coating)in which the treatment liquid composition is sprayed by an ink jetmethod may be mentioned, and any one of those methods may be used. Sincethe treatment liquid composition can be more uniformly adhered to thecloth 2, the treatment liquid composition adhesion step is preferablyperformed by the ink jet coating. In addition, since the degree offreedom of designing the adhesion amount of the treatment liquidcomposition is increased, and since the defects generated when thetreatment liquid composition is adhered are not likely to occur, thetreatment liquid composition is preferably adhered by the roller coatingor the spray coating.

The ink jet printing method according to this embodiment may alsoinclude, after the treatment liquid composition adhesion step isperformed, a treatment liquid composition drying step of drying thetreatment liquid composition adhered to the cloth. Although the dryingof the treatment liquid composition may be performed by spontaneousdrying, in order to increase a drying rate, drying is preferablyperformed with heating. When the treatment liquid composition dryingstep is performed with heating, although the heating method thereof isnot particularly limited, for example, a heat press method, a normalpressure steam method, a high pressure steam method, or a thermofixmethod may be mentioned. In addition, as a heat source of the heating,for example, infrared rays (lamp) may be mentioned.

Although a heating temperature in the drying step is not particularlylimited, for example, the heating temperature is set to preferably 170°C. or less, more preferably 150° C. or less, and further preferably 130°C. or less. Accordingly, even when the cloth is dyed in advance by adispersive dye (sublimation dye), the sublimation of the dispersive dyecaused by the heat drying is suppressed, and in addition, thedegradation in substrate color of the cloth 2 can be suppressed. Inaddition, the lower limit of the heating temperature is not particularlylimited as long as the medium, such as water, contained in the treatmentliquid is evaporated and is preferably set to 100° C. or more.

In addition, when the heating temperature is approximately the same as aheating temperature of heating performed after the ink composition isadhered, which will be described later, it is preferable since thedrying process can be simplified. In this step, the heating temperatureindicates a surface temperature of the treatment liquid compositionadhered to the cloth and, for example, may be measured using anon-contact type thermometer IT2-80 (trade name, available from KeyenceCorporation). A heating time for heating is not particularly limited andis, for example, 30 seconds to 20 minutes.

Ink Composition Adhesion Step

In the ink composition adhesion step, the ink composition used in thisembodiment described above is adhered to the cloth in a region to whichthe treatment liquid composition is adhered. In this step, as the inkcomposition, the ink composition described above is used. Among the inkcompositions, in order to preferably obtain the effect of the presentdisclosure, a pigment-printing ink jet ink composition which contains apigment, resin particles, and water is preferable. In addition, in theink composition adhesion step, a step of adhering a different inkcomposition may also be performed on the region to which the inkcomposition described above is adhered. For example, after a white inkcomposition containing a white pigment is adhered, a color inkcomposition containing a color pigment may be adhered to a region towhich the white ink composition is adhered. When the ink compositionadhesion step includes those two steps, dual layer printing in which animage of the color ink composition is formed on an image formed by thewhite ink composition is recorded. As a method to adhere the inkcomposition to the cloth, an ink jet method is preferably used.

Since the ink jet printing method according to this embodiment includesthe treatment liquid composition adhesion step using the treatmentliquid composition described above, the penetration of the ink adheredin the ink composition adhesion step is preferably suppressed, and theink is allowed to stay on the surface of the cloth. In addition, by areaction or an interaction between the cationic compound of thetreatment liquid composition and the ink components, the ink componentsare aggregated. Hence, a printed material excellent in chromogenicproperty can be obtained.

In the ink composition adhesion step, when the ink composition is awhite ink composition (white pigment-printing ink jet ink composition)containing a white pigment, the maximum adhesion amount thereof to thecloth is set to preferably 50 to 200 mg/cm², more preferably 80 to 150mg/cm², and further preferably 90 to 130 mg/cm². When the maximumadhesion amount of the white ink is set as described above, a whitechromogenic property is improved, and in particular, when the white inkcomposition is adhered to a deep color cloth, the color development isimproved, and the cloth thus obtained is preferably used as a backgroundimage. Since a white image having a preferable color development isprovided under a color image, when being formed on a deep color cloth,the color image has a preferable chromogenic property without receivingthe influence of the color of the cloth. In addition, when the adhesionamount is set in the range described above, the abrasion fastness of theimage is improved, and the aggregate irregularity is preferably notapparent.

On the other hand, in the ink composition adhesion step, when the inkcomposition is a color ink (color pigment-printing ink jet inkcomposition), the maximum adhesion amount thereof to the cloth may beset to 1 to 200 mg/cm², and is preferably 1 to 30 mg/cm², morepreferably 2 to 25 mg/cm², even more preferably 5 to 20 mg/cm², andparticularly preferably 7 to 15 mg/cm². In the case as described above,it is preferable since the chromogenic property of an image to berecorded is improved, the drying property of the image to be recorded isimproved, the image is suppressed from being blurred, and images, suchas pictures and/or letters, can be reproducibly recorded on the cloth.

Heating Step

In the ink jet printing method according to this embodiment, after theink composition adhesion step is performed, a step of heating the clothis preferably performed. By the heating step, the ink composition islikely to uniformly wet spread on the cloth, and in addition, thefixability of the ink composition to the cloth is promoted.

Although a heating method for heating the ink composition applied to thecloth is not particularly limited, for example, a heat press method, anormal pressure steam method, a high pressure steam method, a hot-airdrying method, or a thermofix method may be mentioned.

Although not particularly limited, a heating temperature is preferably100° C. to 200° C. and more preferably 100° C. to 170° C. In addition,when the cloth is formed of cotton, the heating temperature ispreferably 120° C. to 160° C., and when the cloth is formed of apolyester or a polyester blend, the heating temperature is morepreferably 100° C. to 150° C. Since the heating temperature is in therange described above, the reduction of damage on the cloth and the filmformation of the resin particles contained in the ink composition may bepromoted.

In addition, although not particularly limited, a heating time may beset, for example, to 30 seconds to 20 minutes and is preferably 2 to 7minutes and more preferably 3 to 5 minutes. Since the heating time isset in the range described above, while the damage done on the cloth isreduced, the ink can be sufficiently dried. In addition, when theheating temperature described above is approximately the same as theheating temperature of the heating performed after the adhesion of thetreatment liquid composition, the drying process can be preferablysimplified. In this case, the heating temperature of this step indicatesa surface temperature of the treatment liquid composition adhered to thecloth and may be measured, for example, using a non-contact typethermometer IT2-80 (trade name, available from Keyence Corporation).

EXAMPLES

Hereinafter, although the present disclosure will be described in moredetail with reference to Examples, the present disclosure is not limitedthereto.

Preparation of Treatment Liquid Composition

Compositions of treatment liquid compositions of Examples 1 to 49 andComparative Examples 1 to 14 are shown in Tables 1 to 7. The unit of thenumerical value which represents the content of each component in thetable indicates percent by mass and is represented by the rate of theamount of an effective component (solid component). Water is added sothat the total mass of the treatment liquid composition is 100 percentby mass. In addition, the column represented by “-” in which thenumerical value is not described indicates that no component iscontained.

TABLE 1 EXAMPLE 1 2 3 4 5 6 7 8 9 10 TREATMENT CATIONIC POLYVALENT METALCALCIUM 7.0 7.0 7.0 7.0 7.0 7.0 7.0 5.0 7.0 7.0 LIQUID COMPOUND SALTNITRATE COMPOSITION TETRAHYDRATE MAGNESIUM — — — — — — — 3.0 — — SULFATEWATER- MOLECULAR WEIGHT ALKOX E-45 — 0.6 — 2.5 — — — — 0.6 — SOLUBLE OF28,000 TO 2,800,000 PITZCOL K-90 1.0 — 5.0 — 1.0 1.0 1.0 1.0 — 1.0 RESINMOLECULAR WEIGHT ALKOX L-6 — — — — — — — — 1.0 — OF 1,000 TO 25,000PITZCOL K-30 — — — — — — — — — 1.0 — N-VINYL-2- — — — — — — — — — —PYRROLIDONE WATER PARAFFIN WAX AQUACER497 — — — — — — — — — — REPELLANTFLUORINE-BASED SFCOAT SWK- — — — — — — — — — — WATER REPELLANT 601 RESINVINYL ACETATE- VINYBLAN — — — — — — — — — — PARTICLES BASED RESIN 1245LSURFACTANT POLYOXYALKYLENE EMULGEN 350 — — — — — — 1.0 — — — BASEACETYLENE GLYCOL OLFINE E1010 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1BASE WATER BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- ANCE ANCEANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE MOLECULAR WEIGHT PEAK INMOLECULAR WEIGHT RANGE YES YES YES YES YES YES YES YES YES YESDISTRIBUTION OF WATER- OF 28,000 TO 2,800,000 (PEAK A) SOLUBLE COMPONENTPEAK IN MOLECULAR WEIGHT RANGE — — — — — — — — YES YES OF 1,000 TO25,000 (PEAK B) PEAK B AREA/PEAK A AREA — — — — — — — —  1.67  1.00CLOTH PES PES PES PES PES COTTON PES PES PES PES BLEND INK COMPOSITIONINK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 EVALUATIONCHROMOGENIC PROPERTY  B′  B′ A B B S  B′  B′  A′  A′ VISCOSITY A A B B AA A A A A COATING SCAR A A B A B B A A A A STORAGE STABILITY A A A A A AA A A A COATING PROPERTY (SPINNABILITY) A B A B A A A A B A ABRASIONFASTNESS B B B B B B B B B B IRREGULARITY OF COLOR B B B B B B A A B BDEVELOPMENT

TABLE 2 EXAMPLE 11 12 13 14 15 16 17 18 19 20 TREATMENT CATIONICPOLYVALENT METAL CALCIUM 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 LIQUIDCOMPOUND SALT NITRATE COMPOSITION TETRAHYDRATE MAGNESIUM — — — — — — — —— — SULFATE WATER- MOLECULAR WEIGHT ALKOX E-45 0.6 — — — — — — — — —SOLUBLE OF 28,000 TO 2,800,000 PITZCOL K-90 — 1.0 1.0 1.0 1.0 1.0 0.65.0 1.0 1.0 RESIN MOLECULAR WEIGHT ALKOX L-6 — 1.0 — — — — — — — — OF1,000 TO 25,000 PITZCOL K-30 1.0 — 0.2 0.5 3.0 5.0 1.0 1.5 1.0 1.0 —N-VINYL-2- — — — — — — — — — — PYRROLIDONE WATER PARAFFIN WAX AQUACER497— — — — — — — — — — REPELLANT FLUORINE-BASED SFCOAT SWK- — — — — — — — —— — WATER REPELLANT 601 RESIN VINYL ACETATE- VINYBLAN — — — — — — — — —— PARTICLES BASED RESIN 1245L SURFACTANT POLYOXYALKYLENE EMULGEN 350 — —— — — — — — — — BASE ACETYLENE GLYCOL OLFINE E1010 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 BASE WATER BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL-BAL- BAL- ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE MOLECULARWEIGHT PEAK IN MOLECULAR WEIGHT RANGE YES YES YES YES YES YES YES YESYES YES DISTRIBUTION OF WATER- OF 28,000 TO 2,800,000 (PEAK A) SOLUBLECOMPONENT PEAK IN MOLECULAR WEIGHT RANGE YES YES YES YES YES YES YES YESYES YES OF 1,000 TO 25,000 (PEAK B) PEAK B AREA/PEAK A AREA  1.67  1.00 0.20  0.50  3.00  5.00  1.67  0.30  1.00  1.00 CLOTH PES PES PES PESPES PES PES PES PES COTTON BLEND INK COMPOSITION INK 1 INK 1 INK 1 INK 1INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 EVALUATION CHROMOGENIC PROPERTY  A′ A′  B′ B  A′  A′  B′ A S S VISCOSITY A A A A A A A B A A COATING SCAR AA A A A B A B B B STORAGE STABILITY A A A A A A A A A A COATING PROPERTY(SPINNABILITY) B B A A A A A A A A ABRASION FASTNESS B B B B B B B B A AIRREGULARITY OF COLOR B B B B B B B B B B DEVELOPMENT

TABLE 3 EXAMPLE 21 22 23 24 25 26 27 28 29 30 TREATMENT CATIONICPOLYVALENT METAL CALCIUM 7.0 7.0 7.0 5.0 7.0 7.0 7.0 7.0 7.0 7.0 LIQUIDCOMPOUND SALT NITRATE COMPOSITION TETRAHYDRATE MAGNESIUM — — — 3.0 — — —— — — SULFATE WATER- MOLECULAR WEIGHT ALKOX E-45 — 0.6 — — 0.6 1.0 — — —0.6 SOLUBLE OF 28,000 TO 2,800,000 PITZCOL K-90 1.0 — 1.0 1.0 — — 1.01.0 1.0 — RESIN MOLECULAR WEIGHT ALKOX L-6 — 1.0 — — — — — — — — OF1,000 TO 25,000 PITZCOL K-30 1.0 — 1.0 1.0 — — — — — — — N-VINYL-2- — —— — — — 1.0 — — — PYRROLIDONE WATER PARAFFIN WAX AQUACER497 — — — — — —— — 0.1 — REPELLANT FLUORINE-BASED SFCOAT SWK- — — — — — — — 0.1 — 0.1WATER REPELLANT 601 RESIN VINYL ACETATE- VINYBLAN 1.0 1.0 — — 1.0 1.0 —— — — PARTICLES BASED RESIN 1245L SURFACTANT POLYOXYALKYLENE EMULGEN 350— — 1.0 — — — — — — — BASE ACETYLENE GLYCOL OLFINE E1010 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 BASE WATER BAL- BAL- BAL- BAL- BAL- BAL- BAL-BAL- BAL- BAL- ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCEMOLECULAR WEIGHT PEAK IN MOLECULAR WEIGHT RANGE YES YES YES YES YES YESYES YES YES YES DISTRIBUTION OF WATER- OF 28,000 TO 2,800,000 (PEAK A)SOLUBLE COMPONENT PEAK IN MOLECULAR WEIGHT RANGE YES YES YES YES — — — —— — OF 1,000 TO 25,000 (PEAK B) PEAK B AREA/PEAK A AREA  1.00  1.67 1.00  1.00 — — — — — — CLOTH PES PES PES PES PES PES PES PES PES PESINK COMPOSITION INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1INK 1 EVALUATION CHROMOGENIC PROPERTY  A′  A′ B B  B′ B  B′  A′  A′  A′VISCOSITY A A A A A A A A A A COATING SCAR A A A A A A A A A A STORAGESTABILITY A B A A B B A A A B COATING PROPERTY (SPINNABILITY) A B A A BB A A A B ABRASION FASTNESS A A B B A A B B B B IRREGULARITY OF COLOR BB A A B B B C B C DEVELOPMENT

TABLE 4 EXAMPLE 31 32 33 34 35 36 37 38 39 40 TREATMENT CATIONICPOLYVALENT METAL CALCIUM 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 LIQUIDCOMPOUND SALT NITRATE COMPOSITION TETRAHYDRATE MAGNESIUM — — — — — — — —— — SULFATE WATER- MOLECULAR WEIGHT ALKOX E-45 0.6 — — — — — — — — —SOLUBLE OF 28,000 TO 2,800,000 PITZCOL K-90 — 1.0 1.0 1.0 0.6 5.0 1.01.0 1.0 1.0 RESIN MOLECULAR WEIGHT ALKOX L-6 — — — — — — — — — — OF1,000 TO 25,000 PITZCOL K-30 — — — — — — — — — — — N-VINYL-2- — — — — —— — — — — PYRROLIDONE WATER PARAFFIN WAX AQUACER497 0.1 0.01 0.3 0.5 0.10.1 0.1 0.1 0.1 0.1 REPELLANT FLUORINE-BASED SFCOAT SWK- — — — — — — — —— — WATER REPELLANT 601 RESIN VINYL ACETATE- VINYBLAN — — — — — — — —1.0 0.5 PARTICLES BASED RESIN 1245L SURFACTANT POLYOXYALKYLENE EMULGEN350 — — — — — — — — — — BASE ACETYLENE GLYCOL OLFINE E1010 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 BASE WATER BAL- BAL- BAL- BAL- BAL- BAL-BAL- BAL- BAL- BAL- ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCEMOLECULAR WEIGHT PEAK IN MOLECULAR WEIGHT RANGE YES YES YES YES YES YESYES YES YES YES DISTRIBUTION OF WATER- OF 28,000 TO 2,800,000 (PEAK A)SOLUBLE COMPONENT PEAK IN MOLECULAR WEIGHT RANGE — — — — — — — — — — OF1,000 TO 25,000 (PEAK B) PEAK B AREA/PEAK A AREA — — — — — — — — — —CLOTH PES PES PES PES PES PES PES COTTON PES PES BLEND INK COMPOSITIONINK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 EVALUATIONCHROMOGENIC PROPERTY B B  A′  A′  B′ A S S  A′  A′ VISCOSITY A A A A A AA A A A COATING SCAR A A A A A A A B A A STORAGE STABILITY B A A A A B AA A A COATING PROPERTY (SPINNABILITY) B A A A A A A A A A ABRASIONFASTNESS B B B B B B A A A B IRREGULARITY OF COLOR B B B B B B B B B BDEVELOPMENT

TABLE 5 EXAMPLE 41 42 43 44 45 46 47 48 49 TREATMENT CATIONIC POLYVALENTMETAL CALCIUM 7.0 7.0 7.0 7.0 7.0 5.0 7.0 7.0 7.0 LIQUID COMPOUND SALTNITRATE COMPOSITION TETRAHYDRATE MAGNESIUM — — — — — 3.0 — — — SULFATEWATER- MOLECULAR WEIGHT ALKOX E-45 — — — 0.6 — — — 0.6 — SOLUBLE OF28,000 TO 2,800,000 PITZCOL K-90 1.0 1.0 1.0 — 1.0 1.0 1.0 — 1.0 RESINMOLECULAR WEIGHT ALKOX L-6 — — — — — — — 1.0 — OF 1,000 TO 25,000PITZCOL K-30 — — — — — — 1.0 — 1.0 — N-VINYL-2- — — — — — — — — —PYRROLIDONE WATER PARAFFIN WAX AQUACER497 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 REPELLANT FLUORINE-BASED SFCOAT SWK- — — — — — — — — — WATERREPELLANT 601 RESIN VINYL ACETATE- VINYBLAN 3.0 0.3 5.0 1.0 — — — — 1.0PARTICLES BASED RESIN 1245L SURFACTANT POLYOXYALKYLENE EMULGEN 350 — — —— 1.0 — — — — BASE ACETYLENE GLYCOL OLFINE E1010 0.1 0.1 0.1 0.1 — 0.10.1 0.1 0.1 BASE WATER BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- ANCEANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE MOLECULAR WEIGHT PEAK INMOLECULAR WEIGHT RANGE YES YES YES YES YES YES YES YES YES DISTRIBUTIONOF WATER- OF 28,000 TO 2,800,000 (PEAK A) SOLUBLE COMPONENT PEAK INMOLECULAR WEIGHT RANGE — — — — — — YES YES YES OF 1,000 TO 25,000 (PEAKB) PEAK B AREA/PEAK A AREA — — — — — —  1.00  1.67  1.00 CLOTH PES PESPES PES PES PES PES PES PES INK COMPOSITION INK 1 INK 1 INK 1 INK 1 INK1 INK 1 INK 1 INK 1 INK 1 EVALUATION CHROMOGENIC PROPERTY B  A′ B  A′ A′ B A A A VISCOSITY A A A A A A A A A COATING SCAR B A B A A A A A ASTORAGE STABILITY B A B B A A A B A COATING PROPERTY (SPINNABILITY) A AA A A A A B A ABRASION FASTNESS A B A A B B B B A IRREGULARITY OF COLORB B B B A A B B B DEVELOPMENT

TABLE 6 COMPARATIVE EXAMPLE 1 2 3 4 5 6 7 8 9 10 TREATMENT CATIONICPOLYVALENT METAL CALCIUM 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 LIQUIDCOMPOUND SALT NITRATE COMPOSITION TETRAHYDRATE MAGNESIUM — — — — — — — —— — SULFATE WATER- MOLECULAR WEIGHT ALKOX E-45 — — — — — — — — — —SOLUBLE OF 28,000 TO 2,800,000 PITZCOL K-90 0.3 6.0 0.3 6.0 — — — — — —RESIN MOLECULAR WEIGHT ALKOX L-6 — — — — — 1.0 — 3.0 1.0 3.0 OF 1,000 TO25,000 PITZCOL K-30 — — 1.0 1.0 1.0 — 3.0 — — — — N-VINYL-2- — — — — — —— — — — PYRROLIDONE WATER PARAFFIN WAX AQUACER497 — — — — — — — — — —REPELLANT FLUORINE-BASED SFCOAT SWK- — — — — — — — — — — WATER REPELLANT601 RESIN VINYL ACETATE- VINYBLAN — — — — — — — — 1.0 1.0 PARTICLESBASED RESIN 1245L SURFACTANT POLYOXYALKYLENE EMULGEN 350 — — — — — — — —— — BASE ACETYLENE GLYCOL OLFINE E1010 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 BASE WATER BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL- BAL-ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE ANCE MOLECULAR WEIGHT PEAKIN MOLECULAR WEIGHT RANGE YES YES YES YES — — — — — — DISTRIBUTION OFWATER- OF 28,000 TO 2,800,000 (PEAK A) SOLUBLE COMPONENT PEAK INMOLECULAR WEIGHT RANGE — — YES YES YES YES YES YES YES YES OF 1,000 TO25,000 (PEAK B) PEAK B AREA/PEAK A AREA — —  3.33  0.17 — — — — — —CLOTH PES PES PES PES PES PES PES PES PES PES INK COMPOSITION INK 1 INK1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 INK 1 EVALUATION CHROMOGENICPROPERTY C S C S C C C C C C VISCOSITY S C A C S S S A S A COATING SCARA B A B A A B B A B STORAGE STABILITY A A A A A A A A B C COATINGPROPERTY (SPINNABILITY) A A A A A B A B B B ABRASION FASTNESS B B B B BB B B A A IRREGULARITY OF COLOR A B B B B B B B B B DEVELOPMENT

TABLE 7 COMPARATIVE EXAMPLE 11 12 13 14 TREATMENT CATIONIC POLYVALENTCALCIUM 7.0 7.0 7.0 7.0 LIQUID COMPOUND METAL SALT NITRATE COMPOSITIONTETRAHYDRATE MAGNESIUM — — — — SULFATE WATER- MOLECULAR ALKOX E-45 — — —— SOLUBLE WEIGHT OF 28,000 PITZCOL K-90 0.3 6.0 — — RESIN TO 2,800,000MOLECULAR ALKOX L-6 — — — 1.0 WEIGHT OF 1,000 PITZCOL K-30 — — 1.0 — TO25,000 — N-VINYL-2- — — — — PYRROLIDONE WATER PARAFFIN WAX AQUACER4970.1 0.1 0.1 0.1 REPELLANT FLUORINE-BASED SFCOAT SWK- — — — — WATERREPELLANT 601 RESIN VINYL ACETATE- VINYBLAN — — — — PARTICLES BASEDRESIN 1245L SURFACTANT POLYOXYALKYLENE EMULGEN 350 — — — — BASEACETYLENE OLFINE E1010 0.1 0.1 0.1 0.1 GLYCOL BASE WATER BALANCE BALANCEBALANCE BALANCE MOLECULAR WEIGHT PEAK IN MOLECULAR WEIGHT RANGE YES YES— — DISTRIBUTION OF WATER- OF 28,000 TO 2,800,000 (PEAK A) SOLUBLECOMPONENT PEAK IN MOLECULAR WEIGHT RANGE — — YES YES OF 1,000 TO 25,000(PEAK B) PEAK B AREA/PEAK A AREA — — — — CLOTH PES PES PES PES INKCOMPOSITION INK 1 INK 1 INK 1 INK 1 EVALUATION CHROMOGENIC PROPERTY C SC C VISCOSITY S C S S COATING SCAR A B A A STORAGE STABILITY A C A BCOATING PROPERTY (SPINNABILITY) A A A B ABRASION FASTNESS B B B BIRREGULARITY OF COLOR B B B B DEVELOPMENT

In accordance with the compositions shown in Tables to 7, the treatmentliquid compositions of Examples and Comparative Examples were prepared.In particular, after the individual components were charged in acontainer, mixing and stirring were performed for 2 hours using amagnetic stirrer. Subsequently, filtration was performed using apolytetrafluoroethylene (PTFE)-made membrane filter having a pore sizeof 5 μm, so that the treatment liquid composition (hereinafter, alsoreferred to as “treatment liquid” in some cases) of each of Examples andComparative Examples was obtained.

In addition, in Tables 1 to 7, the details of the components notdescribed by the chemical names are as follows. For the componentsdescribed by their chemical names, the respective chemical reagents wereused.

Alkox E-45: trade name, manufactured by Meisei Chemical Works, Ltd.,polyethylene oxide

PITZCOL K-90: trade name, manufactured by DKS Co., Ltd., poly(vinylpyrrolidone)

Alkox L-6: trade name, manufactured by Meisei Chemical Works, Ltd.,polyethylene oxide

PITZCOL K-30: trade name, manufactured by DKS Co., Ltd., poly(vinylpyrrolidone)

AQUACER 497: trade name, manufactured by BYK Japan KK, paraffin waxhaving 50 percent by mass of a solid component and a melting point of60° C.

SFCOAT SWK-601: trade name, manufactured by AGC SEIMI CHEMICAL CO.,LTD., a fluorine-based water repellant having a melting point of morethan 100° C.

Vinyblan 1245L: trade name, manufactured by Nisshin Chemical IndustryCo., Ltd., vinyl acetate/acrylic ester having a solid component of 40%

Emulgen 350: trade name, manufactured by Kao Corporation, apolyoxyethylene stearyl ether, the number of carbon atoms of R⁴ of theformula (1) being 18, and HLB being 17.8

Olfine E1010: trade name “Olfine E1010”, manufactured by NisshinChemical Industry Co., Ltd., acetylene glycol-based surfactant

Water: ion-exchanged water

Molecular Weight Distribution of Water-Soluble Component

After the treatment liquid compositions were each diluted with water toa concentration of 0.1 percent by volume, the measurement was performedunder the following conditions using a gel permeation chromatography(GPC). When the maximum peak was observed in a molecular weight range of28,000 to 2,800,000, in Tables 1 to 7, “yes” is described in the columnof “molecular weight range of 28,000 to 2,800,000”. When the maximumpeak was observed in a molecular weight range of 1,000 to 25,000, inTables 1 to 7, “yes” is described in the column of “molecular weightrange of 1,000 to 25,000”. In addition, the area ratio of a peak B to apeak A was calculated and was described in the column of “peak Barea/peak A area”. In this case, the peak A area indicates the totalarea of peaks present in the molecular weight range of 28,000 to2,800,000, and the peak B area indicates the total area of peaks presentin the molecular weight range of 1,000 to 25,000.

Apparatus: waters alliance

Columns: G5000PW coupled to G3000PW, manufactured by Tosoh Corporation

Mobile Phase: ultrapure water (for LC-MS), manufactured by Wako PureChemical Industries, Ltd.

Flow rate: 1 ml/min

Amount of Sample: 50 μm

Detector: differential refractive index detector

Sample dilution: 0.1% (based on volume)

Filtration before measurement: 0.45-μm filter

Standard Products: poly(ethylene oxide) (calibration curve formed fromseven standard products)

Molecular Weight of Water-Soluble Resin

After the water-soluble resins shown in Tables 1 to were each dilutedwith water to a concentration of 0.1 percent by volume, the measurementwas performed in a manner similar to that of the molecular weightdistribution of the water-soluble component described above. Awater-soluble resin having a primary peak in the molecular weight rangeof 28,000 to 2,800,000 is categorized in the column of “molecular weightof 28,000 to 2,800,000” in Tables 1 to 7, and a water-soluble resinhaving a primary peak in the molecular weight range of 1,000 to 25,000is categorized in the column of “molecular weight of 1,000 to 25,000” inTables 1 to 7.

Preparation of Ink Composition

The composition of an ink composition (ink 1) used for the evaluation ofExamples and Comparative Examples is shown in Table 8. The unit of thenumerical value which represents the content of each component in thetable is percent by mass and is represented by the rate of the amount ofan effective component (solid component). Water was added so that thetotal mass of the ink composition was 100 percent by mass.

TABLE 8 INK COMPOSITION INK 1 COLORANT TITANIUM DIOXIDE SLURRY 40.0RESIN PARTICLES TAKELAC WS-6021 33.0 ORGANIC SOLVENT 2-PYRROLIDONE 2.0GLYCERIN 10.0 TRIETHYLENE GLYCOL 1.0 TRIETHYLENE GLYCOL 1.0 MONOBUTYLETHER SURFACTANT BYK-348 0.3 WATER ION-EXCHANGED WATER BALANCE TOTAL(PERCENT BY MASS) 100.0

In addition, in Table 8, the details of the components not described bythe chemical names are as follows. For the components described by thechemical names, the respective chemical reagents were used.

Titanium oxide slurry: NanoTek® Slurry (trade name, manufactured by C.I.Kasei Co., Ltd., titanium oxide solid component: 20 percent by mass,average particle diameter: 250 nm)

Takelac WS-6021: trade name, manufactured by Mitsui Chemicalspolyurethane, Inc., solid component: 30 percent by mass, urethane-basedresin emulsion

BYK-348: trade name, manufactured by BYK Japan KK, silicone-basedsurfactant (nonionic surfactant)

Water: ion-exchanged water

After the individual components were charged in a container to form thecomposition shown in Table 8, and mixing and stirring were thenperformed for 2 hours using a magnetic stirrer, the mixture thusobtained was sufficiently mixed together by a dispersion treatment usinga bead mill in which zirconia beads each having a diameter of 0.3 mmwere filled. After stirring was performed for 1 hour, filtration wasperformed using a PTFE-made membrane filter having a pore size of 5 μm,so that the ink composition was obtained. The numerical value in Table 8indicates percent by mass, and the purified water (ion-exchanged water)was added so that the total mass of the ink composition was 100 percentby mass.

Formation of Evaluation Cloth Cloth

In Examples and Comparative Examples, the cloths described in Tables 1to 7 were used. The details of the cloths described in the tables are asfollows.

PES: manufactured by Toms Co., Ltd., glimmer ACTIVE WEAR 3.5 oz (tradename), black, 100% of polyester, dry T shirt, L*=17

Cotton: manufactured by Toms Co., Ltd., Printstar Heavy Weight 5.6 oz(trade name), black, 100% of cotton, T shirt, L*=12

PES Blend: manufactured by American Apparel, the 50/50 (trade name),red, 50% of cotton/50% of PES, T shirt, L*=37

Adhesion of Treatment Liquid Composition

The treatment liquid compositions of Examples and Comparative Exampleswere adhered to the respective cloths. As an adhesion method, rollercoating was used, and the treatment liquid composition was sufficientlyimpregnated in a sponge roller. Subsequently, the sponge roller wasrolled on a front surface of a chest region (one-side surface) of the Tshirt used as the cloth four times in a right-to-left direction and atop-to-bottom direction approximately orthogonal thereto, respectively,so that the treatment liquid composition was adhered on the cloth asuniform as possible. In this case, the adhesion amount of the treatmentliquid to the cloth was 20 g per A4 size area.

Next, as a drying step, on the cloth to which the treatment liquidcomposition was adhered, heat drying was performed at 130° C. for 90seconds by a pressing force of 3.0 kN using a heat press machine.Through the drying step, an evaluation cloth treated by the treatmentliquid composition was obtained.

Pigment Printing

Next, by an ink jet method using an ink jet printer SC-F200 (trade name,available from Seiko Epson Corporation), solid printing was performed bythe ink composition on a region to which the treatment liquidcomposition was adhered. In this case, the adhesion amount of the inkcomposition to the cloth was set to 300 g/m².

Subsequently, as the heating step, heat drying was performed at 130° C.for 60 seconds by a pressing force of 3.0 kN using a heat press machine.After the heating step was performed, an evaluation cloth (printedmaterial) on which printing was performed by the ink composition wasobtained.

Evaluation Test

The treatment liquid compositions, the evaluation cloths to each ofwhich the treatment was performed by the treatment liquid composition,and the evaluation cloths to each of which the ink composition wasprinted were evaluated as described below, and the results thereof areshown in Tables 1 to 7.

Chromogenic Property

As the index of the chromogenic property of the white pigment (degree ofwhite), at a region α of the evaluation cloth to which the inkcomposition was adhered, color measurement was performed. In particular,by the use of a colorimeter Spectrolino (available from Gretag MacbethA.G.), the L* value was measured and then evaluated in accordance withthe following criteria. When the chromogenic property was ranked as B′or more, it was evaluated that the effect of the present disclosurecould be obtained.

S: L* value is 90 or more.A: L* value is 85 to less than 90.A′: L* value is 80 to less than 85.B: L* value is 78 to less than 80.B′: L* value is 76 to less than 78.C: L* value is 74 to less than 76.

Viscosity

The viscosity of the treatment liquid composition immediately after thepreparation thereof was measured at 20° C. using a viscoelastic testerMCR-301 (manufactured by Anton Paar) in such a way that the shear ratewas increased from 0.01 to 1.00 s⁻¹, and the viscosity was read at ashear rate of 0.10 s⁻¹. When the evaluation result of the viscosity wasB or more, it was evaluated that the effect of the present disclosurecould be obtained.

S: Viscosity is 1 to less than 5 mPa·s.A: Viscosity is 5 to less than 30 mPa·s.B: Viscosity is 30 to less than 100 mPa·s.C: Viscosity is 100 mPa·s or more.

Coating Scar

Evaluation of a coating scar of the evaluation cloth treated with thetreatment liquid composition was performed. When the treatment liquidcomposition is adhered to the cloth which is colored, in comparison witha portion of the cloth to which the treatment liquid composition is notadhered, the difference in appearance, such as the change in hue, may begenerated as the coating scar in some cases. In this evaluation, aregion β to which the treatment liquid composition was not adhered and aregion γ to which the treatment liquid composition was adhered wereobserved by visual inspection, and the evaluation was performed inaccordance with the following criteria.

A: The difference in appearance between the region β and the region γ ishardly observed.B: The difference in appearance between the region β and the region γ isapparently observed.

Storage Stability

After the treatment liquid composition was prepared, the treatmentliquid composition was left at room temperature for 7 days, and it wasevaluated whether a solid material was separated or not by precipitationor floatation.

A: No separation of solid material occurs.B: Separation of solid material occurs.

Coating Property (Spinnability)

When the treatment liquid composition was applied to the cloth by rollercoating, the coating property was evaluated in accordance with thefollowing criteria.

A: Droplets are neither generated nor scattered.B: Droplets are generated and scattered.

Abrasion Fastness

After the evaluation cloth to which the ink composition was printed waswashed with water and then sufficiently dried, by using a Gakushin-typeabrasion fastness tester AB-301S manufactured by Tester Sangyo Co.,Ltd., an abrasion fastness test was performed by rubbing the cloth 150times with a load of 200 g. Evaluation was based on the level of drytest performed in accordance with Japanese Industrial Standards (JIS)JIS L0849 which confirms the degree of peeling of the ink composition.

A: Level 3 or moreB: less than Level 3

Irregularity of Color Development

By the use of the evaluation cloth to which the ink composition wasprinted, irregularity of color development of the pigment was evaluatedby visual inspection.

A: No granular irregularity of color is observed.B: Although granular irregularity of color is observed, the levelthereof is in an acceptable range.C: Granular irregularity of color is observed, and the level thereof isnot acceptable.

As shown in Tables 1 to 7, according to Examples 1 to 49, it is foundthat the viscosity of the treatment liquid composition is preferable,and a printed material excellent in chromogenic property can beobtained. In addition, the results of the coating scar, the storagestability, the coating property, and the abrasion fastness areexcellent. Furthermore, except for Examples 28 and 30, it is shown thatthe irregularity of color development is suppressed. On the other hand,according to Comparative Examples 1 to 14, it is found that at least oneof the viscosity and the chromogenic property is inferior.

Operation and Effect

Hereinafter, the results derived from this embodiment will be described.

The treatment liquid composition is a treatment liquid composition whichis used to be adhered to a cloth and which contains a cationic compound,a water-soluble resin, and water; the molecular weight distribution of awater-soluble component contained in the treatment liquid compositionhas a maximum peak in a molecular weight range of 28,000 to 2,800,000;and the content of a water-soluble resin having a molecular weight of28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to thetotal mass of the treatment liquid composition.

According to this structure, a treatment liquid composition whichpreferably maintains its viscosity low and which is able to obtain aprinted material excellent in chromogenic property can be obtained. Thereason for this is that since the treatment liquid composition containsthe water-soluble resin, the molecular weight distribution of thewater-soluble component has a maximum peak in a large molecular weightregion of 28,000 to 2,800,000, and the content of the water-solubleresin having a molecular weight of 28,000 to 2,800,000 is 0.6 percent bymass or more with respect to the total mass of the treatment liquidcomposition, the viscosity of an ink composition is increased, thefluidity of the ink composition is degraded, and hence, the inkcomposition is allowed to easily stay on the surface of the cloth.

In more particular, the reason described above will be described in moredetail. When the ink composition is adhered to the cloth to which thetreatment liquid composition is adhered in advance, in the inkcomposition, the water-soluble resin is partially dissolved. Accordingto the water-soluble component in the treatment liquid compositionrepresented by the water-soluble resin, since the molecular weightdistribution thereof has a maximum peak in a relatively large molecularweight range of 28,000 to 2,800,000, when the water-soluble resin isdissolved in the ink composition, the viscosity thereof is increased.Because of the increase in viscosity, the fluidity of the inkcomposition is degraded, and the ink composition is not likely topenetrate in the cloth and is likely to stay on the surface of thecloth.

In addition, besides the water-soluble resin, since the cationiccompound is also contained in the treatment liquid composition, thecationic compound functions to promote the aggregation of the componentsin the ink composition. By the increase in viscosity and the aggregationdescribed above, the ink composition is likely to stay on the surface ofthe cloth, and hence, a preferable color development can be obtained. Inaddition, since the content of the water-soluble resin having amolecular weight of 28,000 to 2,800,000 is 5 percent by mass or lesswith respect to the total mass of the treatment liquid composition, theviscosity of the treatment liquid composition is preferably notexcessively increased.

In the treatment liquid composition described above, the molecularweight distribution of the water-soluble component preferably furtherhas a maximum peak in a molecular weight range of 1,000 to 25,000, andthe peak area of a molecular weight range of 28,000 to U.S. Pat. No.2,800,000 to the peak area of a molecular weight range of 1,000 to25,000 is preferably 1:5 to 5:1.

According to this structure, since the treatment liquid compositionfurther contains a water-soluble component having a relatively smallmolecular weight, the chromogenic property is further improved. Thereason for this is believed that the rate of dissolution of thewater-soluble component having a relatively small molecular weight inthe ink composition is faster than that of a water-soluble componenthaving a large molecular weight. Since the rate of dissolution in theink composition is high, immediately after the adhesion of the inkcomposition, the viscosity of the ink composition tends to be increased,and the ink composition is likely to stay on the surface of the cloth,so that the chromogenic property can be improved.

In the treatment liquid composition, the water-soluble resin ispreferably at least one of a poly(ethylene oxide), a carboxymethylcellulose, a hydroxyethyl cellulose, and a poly(vinyl pyrrolidone).

According to the structure described above, the water-soluble resin ismore likely to be dissolved in the ink composition, and the viscosity ofthe ink composition is likely to be increased. Hence, the inkcomposition is likely to stay on the surface of the cloth, and thechromogenic property can be improved. In addition, in particular, apoly(vinyl pyrrolidone) has a preferable solubility and a lowspinnability and tends to improve the coating property.

The treatment liquid composition described above further preferablycontains a water repellant, and the content of the water repellant withrespect to the total mass of the treatment liquid composition ispreferably 0.01 to 0.30 percent by mass.

According to the structure described above, since a hydrophobic propertyis imparted to the surface of the cloth to which the treatment liquidcomposition is adhered, the ink composition is more likely to stay onthe surface of the cloth, and hence, the chromogenic property can beimproved.

In the treatment liquid composition described above, the water repellantis preferably at least one selected from a fluorine-based waterrepellant, a silicone-based water repellant, and a paraffin wax.

According to the structure described above, the hydrophobic property ispreferably imparted to the surface of the cloth, the ink composition ismore likely to stay on the surface of the cloth, and hence, thechromogenic property can be improved.

In the treatment liquid composition described above, the water repellantis preferably a resin having a melting point of 100° C. or less.

According to the structure described above, the coating property of thetreatment liquid composition is improved. The treatment liquidcomposition can be uniformly adhered, and hence, the irregularity ofcolor development can be suppressed.

In the treatment liquid composition described above, the cloth ispreferably a polyester or a blend containing a polyester and a cotton.

According to the structure described above, for example, by thepolyester or the blend containing a polyester and a cotton, which has alow hydrophilic property as compared to that of cotton, a preferablechromogenic property can be obtained.

In the treatment liquid composition described above, the cloth ispreferably a cloth having a color portion, and the L* value of the colorportion is preferably 80 or less.

According to the structure described above, in the cloth which is deeplycolored, the color (substrate color) of the cloth functioning as anunderlayer is shielded, and the influence of the substrate color is notlikely to be received. Hence, a preferable chromogenic property can beobtained.

The treatment liquid composition described above preferably furthercontains resin particles.

According to the structure described above, the fixability of thecolorant contained in the ink composition is improved. Hence, forexample, the washing fastness and the abrasion fastness of the inkcomposition thus adhered can be improved.

The treatment liquid composition described above preferably furthercontains a nonionic surfactant, and the nonionic surfactant ispreferably a polyoxyethylene oleyl ether.

According to the structure described above, the wet spreadability of theink composition can be improved, and the granularity of an imagerecorded by the ink composition can be suppressed.

In the treatment liquid composition described above, the cationiccompound is preferably a polyvalent metal salt, and the polyvalent metalsalt is preferably at least one selected from calcium nitrate, calciumchloride, and magnesium sulfate.

According to the structure described above, the aggregation of thecomponents in the ink composition is preferably promoted, and apreferable chromogenic property can be obtained.

The treatment liquid composition described above is preferably used forink jet pigment printing.

According to the structure described above, in the ink jet pigmentprinting, a preferable chromogenic property can be obtained.

A set is a set including the treatment liquid composition describedabove and a pigment-printing ink jet ink composition which contains apigment, resin particles, and water.

According to the structure described above, by the treatment liquidcomposition, the chromogenic property of the pigment-printing ink jetink composition can be improved.

In the set described above, the pigment-printing ink jet ink compositionis preferably a white ink containing a white pigment.

According to the structure described above, the chromogenic property ofthe white ink can be improved.

An ink jet printing method is an ink jet printing method which includesa treatment liquid composition adhesion step of adhering the treatmentliquid composition described above to the cloth.

According to the structure described above, by the treatment liquidcomposition, the chromogenic property of the ink jet ink composition canbe improved.

The ink jet printing method described above preferably further includes,after the treatment liquid composition adhesion step is performed, anink composition adhesion step of adhering a pigment-printing ink jet inkcomposition which contains a pigment, resin particles, and water to aregion to which the treatment liquid composition is adhered.

According to the structure described above, by the treatment liquidcomposition, the chromogenic property of the pigment-printing ink jetink composition can be improved.

The cloth is a cloth to which the treatment liquid composition describedabove is adhered.

According to the structure described above, when the ink composition isadhered, a cloth capable of improving the chromogenic property thereofcan be obtained.

The entire disclosure of Japanese Patent Application No. 2018-143267,filed Jul. 31, 2018 is expressly incorporated by reference herein.

What is claimed is:
 1. A treatment liquid composition which is used tobe adhered to a cloth, the treatment liquid composition comprising: acationic compound; a water-soluble resin; and water, wherein a molecularweight distribution of a water-soluble component contained in thetreatment liquid composition has a maximum peak in a molecular weightrange of 28,000 to 2,800,000, and a content of a water-soluble resinhaving a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percentby mass with respect to a total mass of the treatment liquidcomposition.
 2. The treatment liquid composition according to claim 1,wherein the molecular weight distribution of the water-soluble componentfurther has a maximum peak in a molecular weight range of 1,000 to25,000, and a ratio of a peak area of a molecular weight of 28,000 to2,800,000 to a peak area of a molecular weight of 1,000 to 25,000 is 1:5to 5:1.
 3. The treatment liquid composition according to claim 1,wherein the water-soluble resin is at least one selected from apoly(ethylene oxide), a carboxymethyl cellulose, a hydroxyethylcellulose, and a poly(vinyl pyrrolidone).
 4. The treatment liquidcomposition according to claim 1, further comprising a water repellant,wherein a content of the water repellant is 0.01 to 0.30 percent by masswith respect to the total mass of the treatment liquid composition. 5.The treatment liquid composition according to claim 4, wherein the waterrepellant is at least one selected from a fluorine-based waterrepellant, a silicone-based water repellant, and a paraffin wax.
 6. Thetreatment liquid composition according to claim 4, wherein the waterrepellant is a resin having a melting point of 100° C. or less.
 7. Thetreatment liquid composition according to claim 1, wherein the cloth isa polyester or a blend containing a polyester and a cotton.
 8. Thetreatment liquid composition according to claim 1, wherein the cloth hasa color portion, and an L* value of the color portion is 80 or less. 9.The treatment liquid composition according to claim 1, furthercomprising resin particles.
 10. The treatment liquid compositionaccording to claim 1, further comprising a nonionic surfactant, whereinthe nonionic surfactant is a polyoxyethylene oleyl ether.
 11. Thetreatment liquid composition according to claim 1, wherein the cationiccompound is a polyvalent metal salt, and the polyvalent metal salt is atleast one selected from calcium nitrate, calcium chloride, and magnesiumsulfate.
 12. The treatment liquid composition according to claim 1,wherein the treatment liquid composition is used for ink jet pigmentprinting.
 13. A set comprising: the treatment liquid compositionaccording to claim 1; and a pigment-printing ink jet ink compositionwhich contains a pigment, resin particles, and water.
 14. The setaccording to claim 13, wherein the pigment-printing ink jet inkcomposition is a white ink containing a white pigment.
 15. An ink jetprinting method comprising: adhering the treatment liquid compositionaccording to claim 1 to the cloth.
 16. The ink jet printing methodaccording to claim 15, further comprising, after the adhering thetreatment liquid composition is performed, adhering a pigment-printingink jet ink composition which contains a pigment, resin particles, andwater to a region to which the treatment liquid composition is adhered.17. A cloth to which the treatment liquid composition according to claim1 is adhered.